If you mix lines and circles, what happens at the edge of the mixture? The problem is simply stated, but the answer is not obvious. Twenty years ago it was proposed that a universal topological ...driving force would drive cyclic chains to enrich the surface of blends of linear and cyclic chains. Here such behavior is demonstrated experimentally for sufficiently long chains and the limit in molecular weight where packing effects dominate over the topological driving force is identified.
Some synthetic polymers can block cell death when applied following an injury that would otherwise kill the cell. This cellular rescue occurs through interactions of the polymers with cell membranes. ...However, general principles for designing synthetic polymers to ensure strong, but nondisruptive, cell membrane targeting are not fully elucidated. Here, we tailored biomimetic phosphorylcholine-containing block copolymers to interact with cell membranes and determined their efficacy in blocking neuronal death following oxygen-glucose deprivation. By adjusting the hydrophilicity and membrane affinity of poly(2-methacryloyloxyethyl phosphorylcholine) (polyMPC)-based triblock copolymers, the surface active regime in which the copolymers function effectively as membrane-targeting cellular rescue agents was determined. We identified nonintrusive interactions between the polymer and the cell membrane that alter the collective dynamics of the membrane by inducing rigidification without disrupting lipid packing or membrane thickness. In general, our results open new avenues for biological applications of polyMPC-based polymers and provide an approach to designing membrane-targeting agents to block cell death after injury.
The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. ...Due to the interpenetration of the brush with the layer of "untethered chains" a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. The portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. Since these hybrid samples containing a covalently tethered layer at the bottom do not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates, they provide a route for tailoring polymer layer surface properties such as wetting, adhesion and friction.
Surface fluctuations of a layer of polymer chains can be tailored by placing the layer atop a polymer brush with which it interpenetrates.
We report the effects of compressed CO2 molecules as a novel plasticization agent for poly(3-hexylthiophene) (P3HT)-conjugated polymer thin films. In situ neutron reflectivity experiments ...demonstrated the excess sorption of CO2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results proved that these CO2 molecules accelerated the crystallization process of the polymer on the basis of ex situ grazing incidence X-ray diffraction measurements after drying the films via rapid depressurization to atmospheric pressure: both the out-of-plane lamellar ordering of the backbone chains and the intraplane π–π stacking of the side chains were significantly improved, when compared with those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared with those in the thermally annealed counterpart. This is attributed to the CO2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO2 regardless of the type of polymers, the present findings suggest that CO2 annealing near the critical point can be useful as a robust processing strategy for improving the structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer:fullerene bulk heterojunction films.
Moisture attack on adhesive joints is a long-standing scientific and engineering problem. A particularly interesting observation is that when the moisture level in certain systems exceeds a critical ...concentration, the bonded joint shows a dramatic loss of strength. The joint interface plays a dominant role in this phenomenon; however, why a critical concentration of moisture exists and what role is played by the properties of the bulk adhesive have not been adequately addressed. Moreover if the interface is crucial, the local water content near the interface will help elucidate the mechanisms of criticality more than the more commonly examined bulk water concentration in the adhesive. To gain a detailed picture of this criticality, we have combined a fracture mechanics approach to determine joint strength with neutron reflectivity, which provides the moisture distribution near the interface. A well-defined model system, silica glass substrates bonded to a series of polymers based on poly(n-alkyl methacrylate), was utilized to probe the role of the adhesive in a systematic manner. By altering the alkyl chain length, the molecular structure of the polymer can be systematically changed to vary the chemical and physical properties of the adhesive over a relatively wide range. Our findings suggest that the loss of adhesion is dependent on a combination of the build-up of the local water concentration near the interface, interfacial swelling stresses resulting from water absorption, and water-induced weakening of the interfacial bonds. This complexity explains the source of criticality in environmental adhesion failure and could enable design of adhesives to minimize environmental failure.
Sharp dynamic thermal gradient (∇T ≈ 45 °C mm−1) field‐driven assembly of cylinder‐forming block copolymer (c‐BCP) films filled with PS‐coated gold nanoparticles (AuNPs; dNP ≈ 3.6 nm, φNP ≈ 0–0.1) is ...studied. The influence of increasing AuNP loading fraction on dispersion and assembly of AuNPs within c‐BCP (PS‐PMMA) films is investigated via both static and dynamic thermal gradient fields. With φNP increasing, a sharp transition from vertical to random in‐plane horizontal cylinder orientation is observed due to enrichment of AuNPs at the substrate side and favorable interaction of PMMA chains with gold cores. Furthermore, a detachable capping elastomer layer can self‐align these random oriented PMMA microdomains into unidirectional hybrid AuNP/c‐BCP nanolines, quantified with an alignment order parameter, S.
The incorporation of increasing loading fraction of PS‐coated gold nanoparticles into cylinder‐forming block copolymer films induces a facile vertical to random‐in‐plane horizontal morphology transition under dynamic thermal gradient field. Soft‐shear could further align the hybrid nanostructures.
The envelope (E) protein of Dengue virus rearranges to a trimeric hairpin to mediate fusion of the viral and target membranes, which is essential for infectivity. Insertion of E into the target ...membrane serves to anchor E and possibly also to disrupt local order within the membrane. Both aspects are likely to be affected by the depth of insertion, orientation of the trimer with respect to the membrane normal, and the interactions that form between trimer and membrane. In the present work, we resolved the depth of insertion, the tilt angle, and the fundamental interactions for the soluble portion of Dengue E trimers (sE) associated with planar lipid bilayer membranes of various combinations of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-rac-glycerol (POPG), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE), and cholesterol (CHOL) by neutron reflectivity (NR) and by molecular dynamics (MD) simulations. The results show that the tip of E containing the fusion loop (FL) is located at the interface of the headgroups and acyl chains of the outer leaflet of the lipid bilayers, in good agreement with prior predictions. The results also indicate that E tilts with respect to the membrane normal upon insertion, promoted by either the anionic lipid POPG or CHOL. The simulations show that tilting of the protein correlates with hydrogen bond formation between lysines and arginines located on the sides of the trimer close to the tip (K246, K247, and R73) and nearby lipid headgroups. These hydrogen bonds provide a major contribution to the membrane anchoring and may help to destabilize the target membrane.
H-bonds of K246, K247, and R73 with lipid headgroups play a major role in membrane anchoring and cause free trimers to tilt with respect to the membrane upon binding. Display omitted
•Dengue E trimers interact with lipid membranes through hydrogen bonding•Dengue E trimers tilt with respect to the membrane normal and this tilt is correlated with the number of hydrogen bonds•K246, K247, and R73 form a large number hydrogen bonds with lipid headgroups and may be targets for fusion inhibitors•These hydrogen bonding interactions are important for membrane binding and are promoted by both anionic lipids and by cholesterol
We report the effects of compressed CO
molecules as a novel plasticization agent for poly(3-hexylthiophene) (P3HT)-conjugated polymer thin films. In situ neutron reflectivity experiments demonstrated ...the excess sorption of CO
molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results proved that these CO
molecules accelerated the crystallization process of the polymer on the basis of ex situ grazing incidence X-ray diffraction measurements after drying the films via rapid depressurization to atmospheric pressure: both the out-of-plane lamellar ordering of the backbone chains and the intraplane π-π stacking of the side chains were significantly improved, when compared with those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO
-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared with those in the thermally annealed counterpart. This is attributed to the CO
-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO
regardless of the type of polymers, the present findings suggest that CO
annealing near the critical point can be useful as a robust processing strategy for improving the structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer:fullerene bulk heterojunction films.
Many proteins are posttranslationally modified by acylation targeting them to lipid membranes. While methods such as X-ray crystallography and nuclear magnetic resonance are available to determine ...the structure of folded proteins in solution, the precise position of folded domains relative to a membrane remains largely unknown. We used neutron and X-ray reflection methods to measure the displacement of the core domain of HIV Nef from lipid membranes upon insertion of the N-terminal myristate group. Nef is one of several HIV-1 accessory proteins and an essential factor in AIDS progression. Upon insertion of the myristate and residues from the N-terminal arm, Nef transitions from a closed-to-open conformation that positions the core domain 70 Å from the lipid headgroups. This work rules out previous speculation that the Nef core remains closely associated with the membrane to optimize interactions with the cytoplasmic domain of MHC-1.
Display omitted
•Structural insights into membrane-associated HIV-1 Nef•Insertion of the myristate and residues on the N-terminal arm lead to an open form•In the open form, the core domain is displaced 70 Å from the lipid headgroups•When insertion is blocked, membrane-associated Nef is in a closed form
Nef is an HIV-1 accessory protein and an essential factor in AIDS progression. Akgun et al. used neutron and X-ray reflection methods to measure the displacement of the core domain of HIV Nef from lipid membranes upon insertion of the N-terminal myristate.
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