1,005 research outputs found
Lifshitz points in blends of AB and BC diblock copolymers
We consider micro- and macro-phase separation in blends of AB and BC flexible diblock copolymers. We show that, depending on architecture, a number of phase diagram topologies are possible. Microphase separation or macrophase separation can occur, and there are a variety of possible Lifshitz points. Because of the rich parameter space, Lifshitz points of multiple order are possible. We demonstrate Lifshitz points of first and second order, and argue that, in principle, up to 5th-order Lifshitz points are possible
PepMat 2016: The second conference on peptide-based materials for biomedicine and nanotechnology
Postprint (published version
Anomalous structural and mechanical properties of solids confined in quasi one dimensional strips
We show using computer simulations and mean field theory that a system of
particles in two dimensions, when confined laterally by a pair of parallel hard
walls within a quasi one dimensional channel, possesses several anomalous
structural and mechanical properties not observed in the bulk. Depending on the
density and the distance between the walls , the system shows
structural characteristics analogous to a weakly modulated liquid, a strongly
modulated smectic, a triangular solid or a buckled phase. At fixed , a
change in leads to many reentrant discontinuous transitions involving
changes in the number of layers parallel to the confining walls depending
crucially on the commensurability of inter-layer spacing with . The solid
shows resistance to elongation but not to shear. When strained beyond the
elastic limit it fails undergoing plastic deformation but surprisingly, as the
strain is reversed, the material recovers completely and returns to its
original undeformed state. We obtain the phase diagram from mean field theory
and finite size simulations and discuss the effect of fluctuations.Comment: 14 pages, 13 figures; revised version, accepted in J. Chem. Phy
Fmoc–RGDS based fibrils: atomistic details of their hierarchical assembly
We describe the 3D supramolecular structure of Fmoc–RGDS fibrils, where Fmoc and RGDS refer to the hydrophobic N-(fluorenyl-9-methoxycarbonyl) group and the hydrophilic Arg-Gly-Asp-Ser peptide sequence, respectively. For this purpose, we performed atomistic all-atom molecular dynamics simulations of a wide variety of packing modes derived from both parallel and antiparallel ß-sheet configurations. The proposed model, which closely resembles the cross-ß core structure of amyloids, is stabilized by p–p stacking interactions between hydrophobic Fmoc groups. More specifically, in this organization, the Fmoc-groups of ß-strands belonging to the same ß-sheet form columns of p-stacked aromatic rings arranged in a parallel fashion. Eight of such columns pack laterally forming a compact and dense hydrophobic core, in which two central columns are surrounded by three adjacent columns on each side. In addition to such Fmoc¿Fmoc interactions, the hierarchical assembly of the constituent ß-strands involves a rich variety of intra- and inter-strand interactions. Accordingly, hydrogen bonding, salt bridges and p–p stacking interactions coexist in the highly ordered packing network proposed for the Fmoc–RGDS amphiphile. Quantum mechanical calculations, which have been performed to quantify the above referred interactions, confirm the decisive role played by the p–p stacking interactions between the rings of the Fmoc groups, even though both inter-strand and intra-strand hydrogen bonds and salt bridges also play a non-negligible role. Overall, these results provide a solid reference to complement the available experimental data, which are not precise enough to determine the fibril structure, and reconcile previous independent observations.Peer ReviewedPostprint (published version
Analysis of neutron and X-ray reflectivity data. II. Constrained least-squares methods
Micro- vs. macro-phase separation in binary blends of poly(styrene)-poly(isoprene) and poly(isoprene)-poly(ethylene oxide) diblock copolymers
In this paper we present an experimentally determined phase diagram of binary blends of the diblock copolymers poly(styrene)-poly(isoprene) and poly(isoprene)-poly(ethylene oxide). At high temperatures, the blends form an isotropic mixture. Upon lowering the temperature, the blend macro-phase separates before micro-phase separation occurs. The observed phase diagram is compared to theoretical predictions based on experimental parameters. In the low-temperature phase the crystallisation of the poly(ethylene oxide) block influences the spacing of the ordered phase
Multi-scale coarse-graining of diblock copolymer self-assembly: from monomers to ordered micelles
Starting from a microscopic lattice model, we investigate clustering,
micellization and micelle ordering in semi-dilute solutions of AB diblock
copolymers in a selective solvent. To bridge the gap in length scales, from
monomers to ordered micellar structures, we implement a two-step coarse
graining strategy, whereby the AB copolymers are mapped onto ``ultrasoft''
dumbells with monomer-averaged effective interactions between the centres of
mass of the blocks. Monte Carlo simulations of this coarse-grained model yield
clear-cut evidence for self-assembly into micelles with a mean aggregation
number n of roughly 100 beyond a critical concentration. At a slightly higher
concentration the micelles spontaneously undergo a disorder-order transition to
a cubic phase. We determine the effective potential between these micelles from
first principles.Comment: 4 pages, 4 figures, submitted to Phys. Rev. Lett
Monte Carlo Study of the Axial Next-Nearest-Neighbor Ising Model
The equilibrium phase behavior of microphase-forming substances and models is
notoriously difficult to obtain because of the extended metastability of the
modulated phases. We develop a simulation method based on thermodynamic
integration that avoids this problem and with which we obtain the phase diagram
of the canonical three-dimensional axial next-nearest-neighbor Ising model. The
equilibrium devil's staircase, magnetization, and susceptibility are obtained.
The critical exponents confirm the XY nature of the disorder-modulated phase
transition beyond the Lifshitz point. The results identify the limitations of
various approximation schemes used to analyze this basic microphase-forming
model.Comment: 4 pages, 3 figure
Star-Like Micelles with Star-Like Interactions: A quantitative Evaluation of Structure Factor and Phase Diagram
PEP-PEO block copolymer micelles offer the possibility to investigate phase
behaviour and interactions of star polymers (ultra-soft colloids). A star-like
architecture is achieved by an extremely asymmetric block ratio (1:20).
Micellar functionality f can be smoothly varied by changing solvent composition
(interfacial tension). Structure factors obtained by SANS can be quantitatively
described in terms of an effective potential developed for star polymers. The
experimental phase diagram reproduces to a high level of accuracy the predicted
liquid/solid transition. Whereas for intermediate f a bcc phase is observed,
for high f the formation of a fcc phase is preempted by glass formation.Comment: 5 pages, 4 figures, PRL in pres
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