895 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
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
Analysis of neutron and X-ray reflectivity data. II. Constrained least-squares methods
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Interactions between lipid-free apolipoprotein-AI and a lipopeptide incorporating the RGDS cell adhesion motif
The interaction of a designed bioactive lipopeptide C16-GGGRGDS, comprising a hexadecyl lipid chain attached to a functional heptapeptide, with the lipid-free apoliprotein, Apo-AI, is examined. This apolipoprotein
is a major component of high density lipoprotein and it is involved in lipid metabolism and may serve as a biomarker for cardiovascular disease and Alzheimers’ disease. We find via isothermal titration calorimetry that binding between the lipopeptide and Apo-AI occurs up to a saturation condition, just above equimolar for a 10.7 μM concentration of Apo-AI. A similar value is obtained from circular dichroism spectroscopy, which probes the reduction in α-helical secondary structure of Apo-AI upon addition of C16-GGGRGDS. Electron microscopy images show a persistence of fibrillar structures due to self-assembly of C16-GGGRGDS in mixtures with Apo-AI above the saturation binding condition. A small fraction of spheroidal or possibly “nanodisc” structures was observed. Small-angle X-ray scattering (SAXS) data for
Apo-AI can be fitted using a published crystal structure of the Apo-AI dimer. The SAXS data for the lipopeptide/
Apo-AI mixtures above the saturation binding conditions can be fitted to the contribution from fibrillar structures coexisting with flat discs corresponding to Apo-AI/lipopeptide aggregates
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
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
Mesophase formation in two-component cylindrical bottle-brush polymers
When two types of side chains (A,B) are densely grafted to a (stiff) backbone
and the resulting bottle-brush polymer is in a solution under poor solvent
conditions, an incompatibility between A and B leads to microphase separation
in the resulting cylindrical brush. The possible types of ordering are
reminiscent of the ordering of block copolymers in cylindrical confinement.
Starting from this analogy, Leibler's theory of microphase separation in block
copolymer melts is generalized to derive a description of the system in the
weak segregation limit. Also molecular dynamics simulation results of a
corresponding coarse-grained bead-spring model are presented. Using side chain
lengths up to N = 50 effective monomers, the ratio of the Lennard-Jones energy
parameter between unlike monomers and monomers of the same
kind is varied. Various correlation
functions are analyzed to study the conditions when (local) Janus cylinder-type
ordering and when (local) microphase separation in the direction along the
cylinder axis occurs. Both the analytical theory and the simulations give
evidence for short range order due to a tendency towards microphase separation
in the axial direction, with a wavelength proportional to the side chain
gyration radius, irrespective of temperature and grafting density, for a wide
range of these parameters.Comment: 26 pages, 19 figure
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