7,167 research outputs found
Self-Assembly Behavior of Amphiphilic Janus Dendrimers in Water: A Combined Experimental and Coarse-Grained Molecular Dynamics Simulation Approach
Indexación: Scopus.Acknowledgments: M.E.E.G. thank the Ph. D. scholarship (251115) from CONACyT. The authors would like to thank: Luis Elizalde-Herrera (CIQA) for his help running the NMR spectra; Gloria Macedo-Raygoza and Miguel J. Beltrán-GarcÃa (UAG), for their help in the measuring of MALDI-TOF mass spectra; and Maricela RodrÃguez-Nieto and Jorge Luis Menchaca (UANL), for their help with the AFM measurements. FDGN thanks to the USA Air Force Office of Scientific Research Awards.Amphiphilic Janus dendrimers (JDs) are repetitively branched molecules with hydrophilic and hydrophobic components that self-assemble in water to form a variety of morphologies, including vesicles analogous to liposomes with potential pharmaceutical and medical application. To date, the self-assembly of JDs has not been fully investigated thus it is important to gain insight into its mechanism and dependence on JDs’ molecular structure. In this study, the aggregation behavior in water of a second-generation bis-MPA JD was evaluated using experimental and computational methods. Dispersions of JDs in water were carried out using the thin-film hydration and ethanol injection methods. Resulting assemblies were characterized by dynamic light scattering, confocal microscopy, and atomic force microscopy. Furthermore, a coarse-grained molecular dynamics (CG-MD) simulation was performed to study the mechanism of JDs aggregation. The obtaining of assemblies in water with no interdigitated bilayers was confirmed by the experimental characterization and CG-MD simulation. Assemblies with dendrimersome characteristics were obtained using the ethanol injection method. The results of this study establish a relationship between the molecular structure of the JD and the properties of its aggregates in water. Thus, our findings could be relevant for the design of novel JDs with tailored assemblies suitable for drug delivery systems. © 2018 by the authors.https://www.mdpi.com/1420-3049/23/4/96
Toy amphiphiles on the computer: What can we learn from generic models?
Generic coarse-grained models are designed such that they are (i) simple and
(ii) computationally efficient. They do not aim at representing particular
materials, but classes of materials, hence they can offer insight into
universal properties of these classes. Here we review generic models for
amphiphilic molecules and discuss applications in studies of self-assembling
nanostructures and the local structure of bilayer membranes, i.e. their phases
and their interactions with nanosized inclusions. Special attention is given to
the comparison of simulations with elastic continuum models, which are, in some
sense, generic models on a higher coarse-graining level. In many cases, it is
possible to bridge quantitatively between generic particle models and continuum
models, hence multiscale modeling works on principle. On the other side,
generic simulations can help to interpret experiments by providing information
that is not accessible otherwise.Comment: Invited feature article, to appear in Macromolecular Rapid
Communication
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Carbohydrate-derived amphiphilic macromolecules: a biophysical structural characterization and analysis of binding behaviors to model membranes.
The design and synthesis of enhanced membrane-intercalating biomaterials for drug delivery or vascular membrane targeting is currently challenged by the lack of screening and prediction tools. The present work demonstrates the generation of a Quantitative Structural Activity Relationship model (QSAR) to make a priori predictions. Amphiphilic macromolecules (AMs) "stealth lipids" built on aldaric and uronic acids frameworks attached to poly(ethylene glycol) (PEG) polymer tails were developed to form self-assembling micelles. In the present study, a defined set of novel AM structures were investigated in terms of their binding to lipid membrane bilayers using Quartz Crystal Microbalance with Dissipation (QCM-D) experiments coupled with computational coarse-grained molecular dynamics (CG MD) and all-atom MD (AA MD) simulations. The CG MD simulations capture the insertion dynamics of the AM lipophilic backbones into the lipid bilayer with the PEGylated tail directed into bulk water. QCM-D measurements with Voigt viscoelastic model analysis enabled the quantitation of the mass gain and rate of interaction between the AM and the lipid bilayer surface. Thus, this study yielded insights about variations in the functional activity of AM materials with minute compositional or stereochemical differences based on membrane binding, which has translational potential for transplanting these materials in vivo. More broadly, it demonstrates an integrated computational-experimental approach, which can offer a promising strategy for the in silico design and screening of therapeutic candidate materials
Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery
The need to extract oil from wells where it is embedded on the surfaces of
rocks has led to the development of new and improved enhanced oil recovery
techniques. One of those is the injection of surfactants with water vapor,
which promotes desorption of oil that can then be extracted using pumps, as the
surfactants encapsulate the oil in foams. However, the mechanisms that lead to
the optimal desorption of oil and the best type of surfactants to carry out
desorption are not well known yet, which warrants the need to carry out basic
research on this topic. In this work, we report non equilibrium dissipative
particle dynamics simulations of model surfactants and oil molecules adsorbed
on surfaces, with the purpose of studying the efficiency of the surfactants to
desorb hydrocarbon chains, that are found adsorbed over flat surfaces. The
model surfactants studied correspond to nonionic and cationic surfactants, and
the hydrocarbon desorption is studied as a function of surfactant concentration
under increasing Poiseuille flow. We obtain various hydrocarbon desorption
isotherms for every model of surfactant proposed, under flow. Nonionic
surfactants are found to be the most effective to desorb oil and the mechanisms
that lead to this phenomenon are presented and discussed.Comment: 10 figures; to appear in Scientific Report
Field theoretic study of bilayer membrane fusion: I. Hemifusion mechanism
Self-consistent field theory is used to determine structural and energetic
properties of metastable intermediates and unstable transition states involved
in the standard stalk mechanism of bilayer membrane fusion. A microscopic model
of flexible amphiphilic chains dissolved in hydrophilic solvent is employed to
describe these self-assembled structures. We find that the barrier to formation
of the initial stalk is much smaller than previously estimated by
phenomenological theories. Therefore its creation it is not the rate limiting
process. The barrier which is relevant is associated with the rather limited
radial expansion of the stalk into a hemifusion diaphragm. It is strongly
affected by the architecture of the amphiphile, decreasing as the effective
spontaneous curvature of the amphiphile is made more negative. It is also
reduced when the tension is increased. At high tension the fusion pore, created
when a hole forms in the hemifusion diaphragm, expands without bound. At very
low membrane tension, small fusion pores can be trapped in a flickering
metastable state. Successful fusion is severely limited by the architecture of
the lipids. If the effective spontaneous curvature is not sufficiently
negative, fusion does not occur because metastable stalks, whose existence is a
seemingly necessary prerequisite, do not form at all. However if the
spontaneous curvature is too negative, stalks are so stable that fusion does
not occur because the system is unstable either to a phase of stable radial
stalks, or to an inverted-hexagonal phase induced by stable linear stalks. Our
results on the architecture and tension needed for successful fusion are
summarized in a phase diagram.Comment: in press, Biophys.J. accepted versio
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