The influence of steroidal and triterpenoid saponins on monolayer models of the outer leaflets of human erythrocytes, E. coli and S. cerevisiae cell membranes

The present paper discusses the use of monolayers of lipid mixtures mimicking the composition of biological membranes of bacteria, erythrocyte and yeast in the context of the anti-bacterial, hemolytic and anti-fungal activity of saponins. Saponins are plant-produced glycosidic biosurfactants with either steroidal or triterpenoidal aglycone. In the present study we used digitonin as a representative steroidal saponin (extracted from Digitalis purpurea) and a mixture of triterpenoid saponins from Quillaja saponaria Molina. The effect of saponins was studied first on monolayers consisting of single lipids characteristic for the given type of biological membrane, and the

Theory of monolayers with boundaries: Exact results and Perturbative analysis

Domains and bubbles in tilted phases of Langmuir monolayers contain a class of textures knows as boojums. The boundaries of such domains and bubbles may display either cusp-like features or indentations. We derive analytic expressions for the textures within domains and surrounding bubbles, and for the shapes of the boundaries of these regions. The derivation is perturbative in the deviation of the bounding curve from a circle. This method is not expected to be accurate when the boundary suffers large distortions, but it does provide important clues with regard to the influence of various energetic terms on the order-parameter texture and the shape of the domain or bubble bounding curve. We also look into the effects of thermal fluctuations, which include a sample-size-dependent effective line tension.Comment: replaced with published version, 21 pages, 16 figures include

High-Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage

Prussian blue analogues (PBAs) are reported to be efficient sodium storage materials because of the unique advantages of their metal–organic framework structure. However, the issues of low specific capacity and poor reversibility, caused by phase transitions during charge/discharge cycling, have thus far limited the applicability of these materials. Herein, a new approach is presented to substantially improve the electrochemical properties of PBAs by introducing high entropy into the crystal structure. To achieve this, five different metal species are introduced, sharing the same nitrogen-coordinated site, thereby increasing the configurational entropy of the system beyond 1.5R. By careful selection of the elements, high-entropy PBA (HE-PBA) presents a quasi-zero-strain reaction mechanism, resulting in increased cycling stability and rate capability. The key to such improvement lies in the high entropy and associated effects as well as the presence of several active redox centers. The gassing behavior of PBAs is also reported. Evolution of dimeric cyanogen due to oxidation of the cyanide ligands is detected, which can be attributed to the structural degradation of HE-PBA during battery operation. By optimizing the electrochemical window, a Coulombic efficiency of nearly 100% is retained after cycling for more than 3000 cycles

Stabilization of tilt order by chain flexibility in Langmuir monolayers

Langmuir monolayers are modeled as systems of short chains, which are confined to a planar surface at one end, but free to move within the plane. The phase behavior is calculated in a mean field approximation, which combines the self consistent field method with elements of classical density functional theory. It is shown that phases with tilt order are unstable in systems of stiff chains, but can be stabilized by chain conformational entropy in systems of sufficiently flexible chains. The chain entropy is also responsible for the appearance of an additional untilted phase, the liquid expanded phase. The region of stability of the different phases is discussed, and their microscopic structure is analyzed in some detail.Comment: to appear in Phys. Rev.

Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp507826jWe report a joint experimental and theoretical study of the structural and vibrational properties of synthetic sphaerobismoite (beta-Bi2O3) at high pressures in which room-temperature angle-dispersive X-ray diffraction (XRD) and Raman scattering measurements have been complemented with ab initio total energy and lattice dynamics calculations. Striking changes in Raman spectra were observed around 2 GPa, whereas X-ray diffraction measurements evidence no change in the tetragonal symmetry of the compound up to 20 GPa; however, a significant change exists in the compressibility when increasing pressure above 2 GPa. These features have been understood by means of theoretical calculations, which show that beta-Bi2O3 undergoes a pressure-induced isostructural phase transition near 2 GPa. In the new isostructural beta' phase, the Bi3+ and O2- environments become more regular than those in the original beta phase because of the strong decrease in the activity of the lone electron pair of Bi above 2 GPa. Raman measurements and theoretical calculations provide evidence of the second-order nature of the pressure-induced isostructural transition. Above 20 GPa, XRD measurements suggest a partial amorphization of the sample despite Raman measurements still show weak peaks, probably related to a new unknown phase which remains up to 27 GPa. On pressure release, XRD patterns and Raman spectra below 2 GPa correspond to elemental Bi-I, thus evidencing a pressure-induced decomposition of the sample during downstroke.Financial support from the Spanish Consolider Ingenio 2010 Program (MALTA Project CSD2007-00045) is acknowledged. This work was also supported by Brazilian Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) under Project 201050/2012-9, Spanish MICINN under Projects MAT2010-21270-004-01/03/04 and MAT2013-46649-C4-2/3/4-P, Spanish MINECO under Project CTQ2012-36253-C03-02, and from Vicerrectorado de Investigacion de la Universitat Politecnica de Valencia under Projects UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. JAS. acknowledges Juan de la Cierva fellowship program for financial support.Pereira, ALJ.; Sans Tresserras, JÁ.; Vilaplana Cerda, RI.; Gomis, O.; Manjón Herrera, FJ.; Rodriguez-Hernandez, P.; Muñoz, A.... (2014). Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study. Journal of Physical Chemistry C. 118(40):23189-23201. https://doi.org/10.1021/jp507826jS23189232011184

Capacitive energy storage from -50 to 100 °C using an ionic liquid electrolyte

Relying on redox reactions, most batteries are limited in their ability to operate at very low or very high temperatures. While performance of electrochemical capacitors is less dependent on the temperature, present-day devices still cannot cover the entire range needed for automotive and electronics applications under a variety of environmental conditions. We show that the right combination of the exohedral nanostructured carbon (nanotubes and onions) electrode and a eutectic mixture of ionic liquids can dramatically extend the temperature range of electrical energy storage, thus defying the conventional wisdom that ionic liquids can only be used as electrolytes above room temperature. We demonstrate electrical double layer capacitors able to operate from -50 to 100 °C over a wide voltage window (up to 3.7 V) and at very high charge/discharge rates of up to 20 V/s