66 research outputs found
Can adding oil control domain formation in binary amphiphile bilayers?
Bilayers formed of two species of amphiphile of different chain lengths may
segregate into thinner and thicker domains composed predominantly of the
respective species. Using a coarse-grained mean-field model, we investigate how
mixing oil with the amphiphiles affects the structure and thickness of the
bilayer at and on either side of the boundary between two neighbouring domains.
In particular, we find that oil molecules whose chain length is close to that
of the shorter amphiphiles segregate to the thicker domain. This smooths the
surface of the hydrophobic bilayer core on this side of the boundary, reducing
its area and curvature and their associated free-energy penalties. The
smoothing effect is weaker for oil molecules that are shorter or longer than
this optimum value: short molecules spread evenly through the bilayer, while
long molecules swell the thicker domain, increasing the surface area and
curvature of the bilayer core in the interfacial region. Our results show that
adding an appropriate oil could make the formation of domain boundaries more or
less favourable, raising the possibility of controlling the domain size
distribution.Comment: 18 pages including 5 figure
Can amphiphile architecture directly control vesicle size?
Bilayer membranes self-assembled from simple amphiphiles in solution always
have a planar ground-state shape. This is a consequence of several internal
relaxation mechanisms of the membrane and prevents the straightforward control
of vesicle size. Here, we show that this principle can be circumvented and that
direct size control by molecular design is a realistic possibility. Using
coarse-grained calculations, we design tetrablock copolymers that form
membranes with a preferred curvature, and demonstrate how to form
low-polydispersity vesicles while suppressing micellization.Comment: 4 pages, 4 figures. Version 2: Calculations performed for a fuller
range of parameters, accepted for publication in Physical Review Letter
Hydrogen Bonding Aggregation in Acrylamide: Theory and Experiment
Hydrogen bonding plays a role in the microphase separation behavior of many block copolymers, such as those used in lithography, where the stronger interactions due to hydrogen bonding can lead to a smaller period for the self-assembled structures, allowing the production of higher resolution templates. However, current statistical thermodynamic models used in descriptions of microphase separation, such as the FloryâHuggins approach, do not take into account some important properties of hydrogen bonding, such as site specificity and cooperativity. In this combined theoretical and experimental study, a step is taken toward the development of a more complete theory of hydrogen bonding in polymers, using polyacrylamide as a model system. We begin by developing a set of association models to describe hydrogen bonding in amides. Both models with one association constant and two association constants are considered. This theory is used to fit IR spectroscopy data from acrylamide solutions in chloroform, thereby determining the model parameters. We find that models with two constants give better predictions of bond energy in the acrylamide dimer and more realistic asymptotic behavior of the association constants in the limit of high temperatures. At the end of the paper, we briefly discuss the question of the determination of the FloryâHuggins parameter for a diblock copolymer with one self-associating hydrogen bonding block and one non-hydrogen bonding block by means of fitting the scattering function in a disordered state
Heterotelechelic homopolymers mimicking high Ï â ultralow N block copolymers with sub-2 nm domain size
Three fluorinated, hydrophobic initiators have been utilised for the synthesis of low molecular mass fluoro-poly(acrylic acid) heterotelechelic homopolymers to mimic high chi (Ï)âlow N diblock copolymers with ultrafine domains of sub-2 nm length scale. Polymers were obtained by a simple photoinduced copper(II)-mediated reversible-deactivation radical polymerisation (Cu-RDRP) affording low molecular mass (<3 kDa) and low dispersity (Ä = 1.04â1.21) homopolymers. Heating/cooling ramps were performed on bulk samples (ca. 250 ÎŒm thick) to obtain thermodynamically stable nanomorpologies of lamellar (LAM) or hexagonally packed cylinders (HEX), as deduced by small-angle X-ray scattering (SAXS). Construction of the experimental phase diagram alongside a detailed theoretical model demonstrated typical rodâcoil block copolymer phase behaviour for these fluoro-poly(acrylic acid) homopolymers, where the fluorinated initiator-derived segment acts as a rod and the poly(acrylic acid) as a coil. This work reveals that these telechelic homopolymers mimic high Ï-ultralow N diblock copolymers and enables reproducible targeting of nanomorphologies with incredibly small, tunable domain size
Correction: Microphase separation of highly amphiphilic, low N polymers by photoinduced copper-mediated polymerization, achieving sub-2 nm domains at half-pitch
Correction for âMicrophase separation of highly amphiphilic, low N polymers by photoinduced copper-mediated polymerization, achieving sub-2 nm domains at half-pitchâ by Ellis Hancox et al., Polym. Chem., 2019, 10, 6254â6259. DOI: 10.1039/c9py01312a
Microphase separation of highly amphiphilic, low N polymers by photoinduced copper-mediated polymerization, achieving sub-2 nm domains at half-pitch
The lower limit of domain size resolution using microphase separation of short poly(acrylic acid) homopolymers equipped with a short fluorinated tail, posing as an antagonist 'A block' in pseudo AB block copolymers has been investigated. An alkyl halide initiator with a fluorocarbon chain was utilized as a first 'A block' in the synthesis of low molecular weight polymers (1400-4300 g mol -1) using photoinduced Cu(ii)-mediated polymerization allowing for very narrow dispersity. Poly(tert-butyl acrylate) was synthesized and subsequently deprotected to give very low degrees of polymerization (N), amphiphilic polymers with low dispersity (D = 1.06-1.13). By exploiting the high driving force for demixing and the well-defined 'block' sizes, we are able to control the nanostructure in terms of domain size (down to 3.4 nm full-pitch) and morphology. This work demonstrates the simple and highly controlled synthesis of polymers to push the boundaries of the smallest achievable domain sizes obtained from polymer self-assembly
Statistical mechanical approach to secondary processes and structural relaxation in glasses and glass formers
The interrelation of dynamic processes active on separated time-scales in
glasses and viscous liquids is investigated using a model displaying two
time-scale bifurcations both between fast and secondary relaxation and between
secondary and structural relaxation. The study of the dynamics allows for
predictions on the system relaxation above the temperature of dynamic arrest in
the mean-field approximation, that are compared with the outcomes of the
equations of motion directly derived within the Mode Coupling Theory (MCT) for
under-cooled viscous liquids. Varying the external thermodynamic parameters a
wide range of phenomenology can be represented, from a very clear separation of
structural and secondary peak in the susceptibility loss to excess wing
structures.Comment: 13 pages, 8 figure
C60: the first one-component gel?
Until now, gels have been formed of multicomponent soft matter systems,
consisting of a solvent and one or more macromolecular or colloidal species.
Here we show that, for sufficient quench rates, the Girifalco model of C60 can
form gels which we identify by their slow dynamics and long-lived network
structure. These gels are stable at room temperature, at least on the
simulation timescale up to 100 ns. At moderate temperatures around 1000 K,
below the bulk glass transition temperature, C60 exhibits crystallisation and
phase separation proceeds without the dynamical arrest associated with
gelation, in contrast to many colloidal systems.Comment: Accepted by J. Phys. Chem. C. special issue 'Clusters in complex
fluids
Characterization and structural determination of a new anti-MET function-blocking antibody with binding epitope distinct from the ligand binding domain
The growth and motility factor Hepatocyte Growth Factor/Scatter Factor (HGF/SF) and its receptor, the product of the MET proto-oncogene, promote invasion and metastasis of tumor cells and have been considered potential targets for cancer therapy. We generated a new Met-blocking antibody which binds outside the ligand-binding site, and determined the crystal structure of the Fab in complex with its target, which identifies the binding site as the Met Ig1 domain. The antibody, 107_A07, inhibited HGF/SF-induced cell migration and proliferation in vitro and inhibited growth of tumor xenografts in vivo. In biochemical assays, 107_A07 competes with both HGF/SF and its truncated splice variant NK1 for MET binding, despite the location of the antibody epitope on a domain (Ig1) not reported to bind NK1 or HGF/SF. Overlay of the Fab-MET crystal structure with the InternalinB-MET crystal structure shows that the 107_A07 Fab comes into close proximity with the HGF/SF-binding SEMA domain when MET is in the âcompactâ, InternalinB-bound conformation, but not when MET is in the âopenâ conformation. These findings provide further support for the importance of the âcompactâ conformation of the MET extracellular domain, and the relevance of this conformation to HGF/SF binding and signaling
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