Open chain pseudopeptides as hydrogelators with reversible and dynamic responsiveness to pH, temperature and sonication as vehicles for controlled drug delivery

A new family of open chain-pseudopeptidic compounds displaying a pendant carboxylic group have been prepared with excellent yields. Their self-assembly has been studied under different conditions and in different media. Some of the compounds obtained have revealed to act as very efficient hydrogelators at low concentrations (CGC 1 mg mL−1). The resulting hydrogels show some interesting properties, including a high thermal stability, with the hydrogels maintaining their structure at temperatures above 65 °C, and their reversible dynamic sol–gel behavior being responsive to thermal and sonochemical inputs and to changes in the basic/acidic properties of the medium. Preliminary studies for controlled drug delivery have been carried out using a Franz Cell and employing a skin pig membrane, confirming that these Low Molecular Weight Gelators (LMWGs) can be appropriate vehicles for the controlled transdermal delivery of small-molecule drugs.Funding for open access charge: CRUE-Universitat Jaume

Time Scales for transitions between free energy minima of a hard sphere system

Time scales associated with activated transitions between glassy metastable states of a free energy functional appropriate for a dense hard sphere system are calculated by using a new Monte Carlo method for the local density variables. We calculate the time the system,initially placed in a shallow glassy minimum of the free energy, spends in the neighborhood of this minimum before making a transition to the basin of attarction of another free energy minimum. This time scale is found to increase with the average density. We find a crossover density near which this time scale increases very sharply and becomes longer than the longest times accessible in our simulation. This scale shows no evidence of dependence on sample size.Comment: 25 pages, Revtex, 6 postscript figures. Will appear in Phys Rev E, March 1996 or s

On emission-line spectra obtained from evolutionary synthesis models I. Dispersion in the ionising flux and Lowest Luminosity Limits

(abriged) Stellar clusters with the same general physical properties (e.g., total mass, age, and star-formation mode) may have very different stellar mass spectra due to the incomplete sampling of the underlying mass function; such differences are especially relevant in the high-mass tail due to the smaller absolute number of massive stars. The dispersion in the number of massive stars also produces a dispersion in the properties of the corresponding ionising spectra. In this paper, we lay the bases for the future analysis of this effect by evaluating the dispersion in the ionising fluxes of synthetic spectra. As an important consequence, we found that the intensities of synthetic fluxes at different ionisation edges are strongly correlated, a fact suggesting that no additional dispersion will result from the inclusion of sampling effects in the analysis of diagnostic diagrams; this is true for HII regions on all scales. Additionally, we find convincing suggestions that the He II lines are strongly affected by sampling, and so cannot be used to constrain the evolutionary status of stellar clusters. We also establish the range of applicability of synthesis models set by the Lowest Luminosity Limit for the ionising flux, that is the lowest limit in cluster mass for which synthesis models can be applied to predict ionising spectra. This limit marks the boundary between the situations in which the ionising flux is better modeled with a single star as opposed to a star cluster; this boundary depends on the metallicity and age, ranging from 10^3 to more than 10^6 Mo. As a consequence, synthesis models should not be used to try to account for the properties of clusters with smaller masses.Comment: Replaced with accepted versio

Nonlinear Hydrodynamics of a Hard Sphere Fluid Near the Glass Transition

We conduct a numerical study of the dynamic behavior of a dense hard sphere fluid by deriving and integrating a set of Langevin equations. The statics of the system is described by a free energy functional of the Ramakrishnan-Yussouff form. We find that the system exhibits glassy behavior as evidenced through stretched exponential decay and two-stage relaxation of the density correlation function. The characteristic times grow with increasing density according to the Vogel-Fulcher law. The wavenumber dependence of the kinetics is extensively explored. The connection of our results with experiment, mode coupling theory, and molecular dynamics results is discussed.Comment: 34 Pages, Plain TeX, 12 PostScript Figures (not included, available on request

Supramolecularly assisted synthesis of chiral tripodal imidazolium compounds

A strong preference for the formation of tripodal systems over the related monotopic and ditopic compounds is observed for the reaction between tris(halomethyl)benzenes and imidazoles derived from amino acids and containing an amide fragment. This preference allows the formation of the tripodal derivative as the major product even when an equimolar mixture of the tris(halomethyl)benzene and the imidazole is reacted (1 : 1 ratio instead of the stoichiometric 1 : 3 ratio). The reactions were monitored using 1 H NMR spectroscopy and ESI mass spectrometry and kinetically characterized. Computational studies were also performed in order to rationalize the observed preference of the tri-substituted product. The results reveal the existence of well-defined supramolecular interactions between the imidazolium groups and the reacting imidazoles that facilitate the formation of the multitopic systems once the first imidazolium group is formed. Analysis of the different structural components shows that the presence of the amide group from the amino acid moiety is the key structural requirement for such supramolecular assistance to take place. The preorganization of the supramolecular intermediates formed through hydrogen bonding interactions involving amide-NH fragments in imidazoles and bromide anions in imidazolium groups seems to be also present at the corresponding TSs, decreasing the associated energy barriers

Entropic Origin of the Growth of Relaxation Times in Simple Glassy Liquids

Transitions between ``glassy'' local minima of a model free-energy functional for a dense hard-sphere system are studied numerically using a ``microcanonical'' Monte Carlo method that enables us to obtain the transition probability as a function of the free energy and the Monte Carlo ``time''. The growth of the height of the effective free energy barrier with density is found to be consistent with a Vogel-Fulcher law. The dependence of the transition probability on time indicates that this growth is primarily due to entropic effects arising from the difficulty of finding low-free-energy saddle points connecting glassy minima.Comment: Four pages, plus three postscript figure

Proceedings of the First Annual Workshop of the HORIZON 2020 CEBAMA Project (KIT Scientific Reports ; 7734)

The Proceedings of the First Annual Workshop of the Collaborative Project CEBAMA addresses key scientific questions related to the use of cement-based materials in nuclear waste disposal applications. Progress beyond the state-of-the-art is achieved by providing basic knowledge, new experimental data, improved modeling and arguments for the Nuclear Waste Disposal Safety Case. CEBAMA is funded by the European Commission under the Horizon 2020 frame of EURATOM

Renormalization Group Study of the Intrinsic Finite Size Effect in 2D Superconductors

Vortices in a thin-film superconductor interact logarithmically out to a distance on the order of the two-dimensional (2D) magnetic penetration depth $\lambda_\perp$, at which point the interaction approaches a constant. Thus, because of the finite $\lambda_\perp$, the system exhibits what amounts to an {\it intrinsic} finite size effect. It is not described by the 2D Coulomb gas but rather by the 2D Yukawa gas (2DYG). To study the critical behavior of the 2DYG, we map the 2DYG to the massive sine-Gordon model and then perform a renormalization group study to derive the recursion relations and to verify that $\lambda_\perp$ is a relevant parameter. We solve the recursion relations to study important physical quantities for this system including the renormalized stiffness constant and the correlation length. We also address the effect of current on this system to explain why finite size effects are not more prevalent in experiments given that the 2D magnetic penetration depth is a relevant parameter.Comment: 8 pages inRevTex, 5 embedded EPS figure