Estudio de interacciones de AgNPs con monocapas de dimiristoilfosfatidilcolina

El uso de nanopartículas (NPs) sintéticas se ha incrementado enormemente en los últimos años debido a su creciente uso en aplicaciones biomédicas y en nanomedicina. Por este motivo, resulta sumamente importante el estudio de las interacciones entre NPs con membranas celulares. En muchos casos las NPs necesitan unirse, romper y penetrar la membrana celular para inducir una respuesta, lo cual depende fuertemente de su tamaño, forma, carga superficial y funcionalidad química superficial. Las NPs con dimensiones menores que 2 nm pueden penetrar en las membranas celulares mientras que para las de mayor tamaño se ha propuesto que su acción ocurre principalmente a través de alteraciones de la estructura de la membrana, lo cual puede afectar fuertemente su permeabilidad, el potencial de membrana y sus funciones principales. Dependiendo entonces de la acción propuesta para las NPs en los sistemas biológicos es imprescindible el conocimiento de su interacción con las membranas.Se planteó estudiar la adsorción de AgNPs modificadas con citrato (AgNPs–CT) y con ácido 4-mercaptobenzoico (AgNPs–MBA) en ausencia y presencia de monocapas de dimiristoilfosfatidilcolina (DMPC) e investigar la capacidad de las AgNPs–CT y AgNPs–MBA para formar monocapas de Langmuir por sí mismas y en contacto con DMPC a distintos grados de empaquetamiento.Para estudiar la interacción de AgNPs–CT y con AgNPs–MBA con un modelo de biomembrana, se evaluó la adsorción de las NPs a la interfase agua/aire y a interfases de DMPC a diferentes presiones de superficie (p), a fin de conocer si la organización bidimensional que posee el lípido en la interfase condiciona la interacción con las AgNPs.Se observó interacción con DMPC por parte de todas las AgNPs (Citratadas y con MBA). Cuando la p de DMPC fue 5mN/m, la presencia de NPs produjo un incremento en la presión de 5-7.5mN/m, lo cual indica interacción con el lípido. Cuando la presión de DMPC fue 30mN/m, las NPs no produjeron cambios en p, indicando ausencia de interacción.Por otro lado, se comparó la isoterma de Langmuir de DMPC pura con las isotermas de DMPC en las que se adsorbieron AgNPs–CT y AgNPs–MBA. La interacción de AgNPs–MBA con DMPC produce una expansión del área en toda la isoterma que es prácticamente constante y representa un incremento en el área, respecto a DMPC pura. Por su parte, la presencia de MBA en la subfase no produce cambios en el área que ocupa DMPC. Las AgNPs–CT producen una pequeña modificación en el área que ocupa DMPC (respecto a cuando está pura) hasta aproximadamente 20mN/m, luego las isotermas prácticamente se superponen indicando que las NPs que estaban en la interfase son excluídas.De acuerdo a los resultados obtenidos, tanto AgNPs–CT como AgNPs–MBA, interaccionan con el DMPC a temperatura ambiente. Se observó que la magnitud de interacción AgNPs/DMPC depende de la p a la cual se encuentra el fosfolípido. Siendo una clara evidencia, de que la organización del lípido en la monocapa (o interfase y posiblemente en biomembranas) es un factor clave que regula la interacción

Nanoemulsions of synthetic rhamnolipids act as plant resistance inducers without damaging plant tissues or affecting soil microbiota

Plant pathogens and pests can cause significant losses in crop yields, affecting food security and the global economy. Many traditional chemical pesticides are used to combat these organisms. This can lead to the development of pesticide-resistant strains of pathogens/insects and negatively impact the environment. The development of new bioprotectants, which are less harmful to the environment and less likely to lead to pesticide-resistance, appears as a sustainable strategy to increase plant immunity. Natural Rhamnolipids (RL-Nat) are a class of biosurfactants with bioprotectant properties that are produced by an opportunistic human pathogen bacterium. RL-Nat can act as plant resistance inducers against a wide variety of pathogens. Recently, a series of bioinspired synthetic mono-RLs produced by green chemistry were also reported as phytoprotectants. Here, we explored their capacity to generate novel colloidal systems that might be used to encapsulate bioactive hydrophobic compounds to enhance their performance as plant bioprotectants. The synthetic mono-RLs showed good surfactant properties and emulsification power providing stable nanoemulsions capable of acting as bio-carriers with good wettability. Synthetic RLs-stabilized nanoemulsions were more effective than RLs suspensions at inducing plant immunity, without causing deleterious effects. These nanoemulsions were innocuous to native substrate microbiota and beneficial soil-borne microbes, making them promising safe bio-carriers for crop protection

Estudio de interacciones de AgNPs con monocapas de dimiristoilfosfatidilcolina

El uso de nanopartículas (NPs) sintéticas se ha incrementado enormemente en los últimos años debido a su creciente uso en aplicaciones biomédicas y en nanomedicina. Por este motivo, resulta sumamente importante el estudio de las interacciones entre NPs con membranas celulares. En muchos casos las NPs necesitan unirse, romper y penetrar la membrana celular para inducir una respuesta, lo cual depende fuertemente de su tamaño, forma, carga superficial y funcionalidad química superficial. Las NPs con dimensiones menores que 2 nm pueden penetrar en las membranas celulares mientras que para las de mayor tamaño se ha propuesto que su acción ocurre principalmente a través de alteraciones de la estructura de la membrana, lo cual puede afectar fuertemente su permeabilidad, el potencial de membrana y sus funciones principales. Dependiendo entonces de la acción propuesta para las NPs en los sistemas biológicos es imprescindible el conocimiento de su interacción con las membranas.Se planteó estudiar la adsorción de AgNPs modificadas con citrato (AgNPs–CT) y con ácido 4-mercaptobenzoico (AgNPs–MBA) en ausencia y presencia de monocapas de dimiristoilfosfatidilcolina (DMPC) e investigar la capacidad de las AgNPs–CT y AgNPs–MBA para formar monocapas de Langmuir por sí mismas y en contacto con DMPC a distintos grados de empaquetamiento.Para estudiar la interacción de AgNPs–CT y con AgNPs–MBA con un modelo de biomembrana, se evaluó la adsorción de las NPs a la interfase agua/aire y a interfases de DMPC a diferentes presiones de superficie (p), a fin de conocer si la organización bidimensional que posee el lípido en la interfase condiciona la interacción con las AgNPs.Se observó interacción con DMPC por parte de todas las AgNPs (Citratadas y con MBA). Cuando la p de DMPC fue 5mN/m, la presencia de NPs produjo un incremento en la presión de 5-7.5mN/m, lo cual indica interacción con el lípido. Cuando la presión de DMPC fue 30mN/m, las NPs no produjeron cambios en p, indicando ausencia de interacción.Por otro lado, se comparó la isoterma de Langmuir de DMPC pura con las isotermas de DMPC en las que se adsorbieron AgNPs–CT y AgNPs–MBA. La interacción de AgNPs–MBA con DMPC produce una expansión del área en toda la isoterma que es prácticamente constante y representa un incremento en el área, respecto a DMPC pura. Por su parte, la presencia de MBA en la subfase no produce cambios en el área que ocupa DMPC. Las AgNPs–CT producen una pequeña modificación en el área que ocupa DMPC (respecto a cuando está pura) hasta aproximadamente 20mN/m, luego las isotermas prácticamente se superponen indicando que las NPs que estaban en la interfase son excluídas.De acuerdo a los resultados obtenidos, tanto AgNPs–CT como AgNPs–MBA, interaccionan con el DMPC a temperatura ambiente. Se observó que la magnitud de interacción AgNPs/DMPC depende de la p a la cual se encuentra el fosfolípido. Siendo una clara evidencia, de que la organización del lípido en la monocapa (o interfase y posiblemente en biomembranas) es un factor clave que regula la interacción

Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

An anhydrous 1:1 crystalline inclusion complex between the organophosphorus insecticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate] and the host compound heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) was prepared and its structure elucidated by single-crystal X-ray diffraction. This revealed two independent host molecules in the asymmetric unit. In one of these, the cavity is occupied by two disordered guest components (distinguishable as rotamers with respect to the P–OAr bond) while in the other, three distinct guest components with site-occupancies 0.44, 0.29 and 0.27 appear, the last having a reversed orientation relative to all the other components. Kinetic studies of the alkaline hydrolysis of fenitrothion in the presence of DIMEB showed a remarkable reduction of 84% in the rate of this reaction relative to that for the free substrate, a value exceeding those previously attained with the native hosts, β- and γ-cyclodextrin, and fully methylated β-cyclodextrin

Cavity Orientation Regulated by Mixture Composition and Clustering of Amphiphilic Cyclodextrins in Phospholipid Monolayers

Artificial supramolecular-hierarchical structures that emulate nature represent an overcoming alternative for the design of new drug delivery systems. Thermodynamic and topographic properties of films formed by a monoacylated amphiphilic β-cyclodextrin (βCD-C16) with the phospholipid 1-palmitoyl-2-oleoyl-<i>sn</i>-glycero-3-phosphocholine (POPC) at the air/water interface were studied. βCD-C16 formed stable mixed films with POPC at several proportions when spread together at the air/water interface. The orientation of βCD-C16 cavity at the interface depends on its mole fraction in the film as reveled by the analysis of partial mean molecular areas as a function of composition. Furthermore, βCD-C16 was able to penetrate POPC preformed films in a broad range of initial surface pressures, including that near the collapse pressure of the phospholipid. These results demonstrated the strong tendency of βCD-C16 to be inserted into this lipid matrix commonly used in liposome formulations. Topography studies show that βCD-C16 segregate from POPC forming clusters enriched in βCD-C16. Segregation of βCD-C16 was especially noticeable when βCD-C16 were incorporated by themselves into a preformed POPC matrix leading to ordered and highly birefringent structures that suggest the formation of hierarchical stacked βCD-C16 arrangement at the interface

The Rheological Properties of Lipid Monolayers Modulate the Incorporation of l‑Ascorbic Acid Alkyl Esters

In this work, we tested the hypothesis that the incorporation of amphiphilic drugs into lipid membranes may be regulated by their rheological properties. For this purpose, two members of the l-ascorbic acid alkyl esters family (ASC_<i>n</i>) were selected, ASC₁₆ and ASC₁₄, which have different rheological properties when organized at the air/water interface. They are lipophilic forms of vitamin C used in topical pharmacological preparations. The effect of the phase state of the host lipid membranes on ASC_<i>n</i> incorporation was explored using Langmuir monolayers. Films of pure lipids with known phase states have been selected, showing liquid-expanded, liquid-condensed, and solid phases as well as pure cholesterol films in liquid-ordered state. We also tested ternary and quaternary mixed films that mimic the properties of cholesterol containing membranes and of the stratum corneum. The compressibility and shear properties of those monolayers were assessed in order to define its phase character. We found that the length of the acyl chain of the ASC_<i>n</i> compounds induces differential changes in the rheological properties of the host membrane and subtly regulates the kinetics and extent of the penetration process. The capacity for ASC_<i>n</i> uptake was found to depend on the phase state of the host film. The increase in surface pressure resultant after amphiphile incorporation appears to be a function of the capacity of the host membrane to incorporate such amphiphile as well as the rheological response of the film. Hence, monolayers that show a solid phase state responded with a larger surface pressure increase to the incorporation of a comparable amount of amphiphile than liquid-expanded ones. The cholesterol-containing films, including the mixture that mimics stratum corneum, allowed a very scarce ASC_<i>n</i> uptake independently of the membrane diffusional properties. This suggests an important contribution of Cho on the maintenance of the barrier function of stratum corneum

Distinctive Interactions of Oleic Acid Covered Magnetic Nanoparticles with Saturated and Unsaturated Phospholipids in Langmuir Monolayers

The growing number of innovations in nanomedicine and nanobiotechnology are posing new challenges in understanding the full spectrum of interactions between nanomateriales and biomolecules at nano-biointerfaces. Although considerable achievements have been accomplished by in vivo applications, many issues regarding the molecular nature of these interactions are far from being well-understood. In this work, we evaluate the interaction of hydrophobic magnetic nanoparticles (MNP) covered with a single layer of oleic acid with saturated and unsaturated phospholipids found in biomembranes through the use of Langmuir monolayers. We find distinctive interactions among the MNP with saturated and unsaturated phospholipids that are reflected by both, the compression isotherms and the surface topography of the films. The interaction between MNP and saturated lipids causes a noticeable reduction of the mean molecular area in the interfacial plane, while the interaction with unsaturated lipids promotes area expansion compared to the ideally mixed films. Moreover, when liquid expanded and liquid condensed phases of the phospholipid(s) coexist, the MNP preferably partition to the liquid-expanded phase, thus hindering the coalescence of the condensed domains with increasing surface pressure. In consequence organizational information on long-range order is attained. These results evidence the existence of a sensitive composition-dependent surface regulation given by phospholipid–nanoparticle interactions which enhance the biophysical relevance of understanding nanoparticle surface functionalization in relation to its interactions in biointerfaces constituted by defined types of biomolecules

The CARMENES search for exoplanets around M dwarfs: First visual-channel radial-velocity measurements and orbital parameter updates of seven M-dwarf planetary systems

The appendix tables are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/609/A117Context. The main goal of the CARMENES survey is to find Earth-mass planets around nearby M-dwarf stars. Seven M dwarfs included in the CARMENES sample had been observed before with HIRES and HARPS and either were reported to have one short period planetary companion (GJ 15 A, GJ 176, GJ 436, GJ 536 and GJ 1148) or are multiple planetary systems (GJ 581 and GJ 876). Aims. We aim to report new precise optical radial velocity measurements for these planet hosts and test the overall capabilities of CARMENES. Methods. We combined our CARMENES precise Doppler measurements with those available from HIRES and HARPS and derived new orbital parameters for the systems. Bona-fide single planet systems were fitted with a Keplerian model. The multiple planet systems were analyzed using a self-consistent dynamical model and their best fit orbits were tested for long-term stability. Results. We confirm or provide supportive arguments for planets around all the investigated stars except for GJ 15 A, for which we find that the post-discovery HIRES data and our CARMENES data do not show a signal at 11.4 days. Although we cannot confirm the super-Earth planet GJ 15 Ab, we show evidence for a possible long-period (P = 7030 d) Saturn-mass (msini = 51.8M) planet around GJ 15 A. In addition, based on our CARMENES and HIRES data we discover a second planet around GJ 1148, for which we estimate a period P = 532.6 days, eccentricity e = 0.342 and minimum mass msini = 68.1M. Conclusions. The CARMENES optical radial velocities have similar precision and overall scatter when compared to the Doppler measurements conducted with HARPS and HIRES. We conclude that CARMENES is an instrument that is up to the challenge of discovering rocky planets around low-mass stars.© ESO, 2018.CARMENES is an instrument for the Centro Astronomico Hispano-Aleman de Calar Alto (CAHA, Almeria, Spain). CARMENES is funded by the German Max-Planck-Gesellschaft (MPG), the Spanish Consejo Superior de Investigaciones Cientificas (CSIC), the European Union through FEDER/ERF FICTS-2011-02 funds, and the members of the CARMENES Consortium (Max-Planck-Institut fur Astronomie, Instituto de Astrofisica de Andalucia, Landessternwarte Konigstuhl, Institut de Ciencies de l'Espai, Insitut fur Astrophysik Gottingen, Universidad Complutense de Madrid, Thuringer Landessternwarte Tautenburg, Instituto de Astrofisica de Canarias, Hamburger Sternwarte, Centro de Astrobiologia and Centro Astronomico Hispano-Aleman), with additional contributions by the Spanish Ministry of Economy, the German Science Foundation (DFG), the Klaus Tschira Stiftung, the states of Baden-Wurttemberg and Niedersachsen, the DFG Research Unit FOR2544 >Blue Planets around Red Stars>, and by the Junta de Andalucia. This work has made use of data from the European Space Agency (ESA) mission Gaia (https://www.cosmos.esa.int/gaia), processed by the Gaia Data Processing and Analysis Consortium (DPAC, https://www.cosmos.esa.int/web/gaia/dpac/consortium). Funding for the DPAC has been provided by national institutions, in particular the institutions participating in the Gaia Multilateral Agreement. This work used the Systemic Console package (Meschiari et al. 2009) for cross-checking our Keplerian and Dynamical fits and the python package astroML (VanderPlas et al. 2012) for the calculation of the GLS periodogram. The IEEC-CSIC team acknowledges support by the Spanish Ministry of Economy and Competitiveness (MINECO) and the Fondo Europeo de Desarrollo Regional (FEDER) through grant ESP2016-80435-C2-1-R, as well as the support of the Generalitat de Catalunya/CERCA programme. The IAA-CSIC team acknowledges support by the Spanish Ministry of Economy and Competitiveness (MINECO) through grants AYA2014-54348-C03-01 and AYA2016-79425-C3-3-P as well as FEDER funds. The UCM team acknowledges support by the Spanish Ministry of Economy and Competitiveness (MINECO) from projects AYA2015-68012-C2-2-P and AYA2016-79425- C3-1,2,3-P and the Spanish Ministerio de Educacion, Cultura y Deporte, programa de Formacion de Profesorado Universitario, under grant FPU15/01476. T. T. and M.K. thank to Jan Rybizki for the very helpful discussion in the early phases of this work. V.J.S.B. is supported by grant AYA2015-69350-C3-2-P from the Spanish Ministry of Economy and Competiveness (MINECO). J.C.S. acknowledges funding support from Spanish public funds for research under project ESP2015-65712-C5-5-R (MINECO/FEDER), and under Research Fellowship program >Ramon y Cajal> with reference RYC2012-09913 (MINECO/FEDER). The contributions of M.A. were supported by DLR (Deutsches Zentrum fur Luft- und Raumfahrt) through the grants 50OW0204 and 50OO1501. J.L.-S. acknowledges the Office of Naval Research Global (award No. N62909-15- 1-2011) for support. C.d.B. acknowledges that this work has been supported by Mexican CONACyT research grant CB-2012-183007 and the Spanish Ministry of Economy and Competitivity through projects AYA2014-54348-C3-2-R. J.I.G.H., and R.R. acknowledge financial support from the Spanish Ministry project MINECO AYA2014-56359-P. J.I.G.H. also acknowledges financial support from the Spanish MINECO under the 2013 Ramon y Cajal program MINECO RYC-2013-14875. V. Wolthoff acknowledges funding from the DFG Research Unit FOR2544 >Blue Planets around Red Stars>, project No. RE 2694/4-1.We thank the anonymous referee for the excellent comments that helped to improve the quality of this paper

The CARMENES search for exoplanets around M dwarfs: High-resolution optical and near-infrared spectroscopy of 324 survey stars

The CARMENES radial velocity (RV) survey is observing 324 M dwarfs to search for any orbiting planets. In this paper, we present the survey sample by publishing one CARMENES spectrum for each M dwarf. These spectra cover the wavelength range 520¿1710 nm at a resolution of at least R >80 000, and we measure its RV, H¿ emission, and projected rotation velocity. We present an atlas of high-resolution M-dwarf spectra and compare the spectra to atmospheric models. To quantify the RV precision that can be achieved in low-mass stars over the CARMENES wavelength range, we analyze our empirical information on the RV precision from more than 6500 observations. We compare our high-resolution M-dwarf spectra to atmospheric models where we determine the spectroscopic RV information content, Q, and signal-to-noise ratio. We find that for all M-type dwarfs, the highest RV precision can be reached in the wavelength range 700¿900 nm. Observations at longer wavelengths are equally precise only at the very latest spectral types (M8 and M9). We demonstrate that in this spectroscopic range, the large amount of absorption features compensates for the intrinsic faintness of an M7 star. To reach an RV precision of 1 m s¿1 in very low mass M dwarfs at longer wavelengths likely requires the use of a 10 m class telescope. For spectral types M6 and earlier, the combination of a red visual and a near-infrared spectrograph is ideal to search for low-mass planets and to distinguish between planets and stellar variability. At a 4 m class telescope, an instrument like CARMENES has the potential to push the RV precision well below the typical jitter level of 3-4 m s-1. © ESO 2018.We thank an anonymous referee for prompt attention and helpful comments that helped to improve the quality of this paper. CARMENES is an instrument for the Centro Astronomico Hispano-Aleman de Calar Alto (CAHA, Almeria, Spain). CARMENES is funded by the German Max-Planck-Gesellschaft (MPG), the Spanish Consejo Superior de Investigaciones Cientificas (CSIC), the European Union through FEDER/ERF FICTS-2011-02 funds, and the members of the CARMENES Consortium (Max-Planck-Institut fur Astronomie, Instituto de Astrofisica de Andalucia, Landessternwarte Konigstuhl, Institut de Ciencies de l'Espai, Insitut fur Astrophysik Gottingen, Universidad Complutense de Madrid, Thuringer Landessternwarte Tautenburg, Instituto de Astrofisica de Canarias, Hamburger Sternwarte, Centro de Astrobiologia and Centro Astronomico Hispano-Aleman), with additional contributions by the Spanish Ministry of Economy, the German Science Foundation through the Major Research Instrumentation Programme and DFG Research Unit FOR2544 >Blue Planets around Red Stars>, the Klaus Tschira Stiftung, the states of Baden-Wurttemberg and Niedersachsen, and by the Junta de Andalucia. This work has made use of the VALD database, operated at Uppsala University, the Institute of Astronomy RAS in Moscow, and the University of Vienna. We acknowledge the following funding programs: European Research Council (ERC-279347), Deutsche Forschungsgemeinschaft (RE 1664/12-1, RE 2694/4-1), Bundesministerium fur Bildung und Forschung (BMBF-05A14MG3, BMBF-05A17MG3), Spanish Ministry of Economy and Competitiveness (MINECO, grants AYA2015-68012-C2-2-P, AYA2016-79425-C3-1,2,3-P, AYA2015-69350-C3-2-P, AYA2014-54348-C03-01, AYA2014-56359-P, AYA2014-54348-C3-2R, AYA2016-79425-C3-3-P and 2013 Ramon y Cajal program RYC-2013-14875), Fondo Europeo de Desarrollo Regional (FEDER, grant ESP2016-80435-C2-1-R, ESP2015-65712-C5-5-R), Generalitat de Catalunya/CERCA programme, Spanish Ministerio de Educacion, Cultura y Deporte, programa de Formacion de Profesorado Universitario (grant FPU15/01476), Deutsches Zentrum fur Luft- und Raumfahrt (grants 50OW0204 and 50OO1501), Office of Naval Research Global (award no. N62909-15-1-2011), Mexican CONACyT grant CB-2012-183007