2-Dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) is a chelating, amphoteric surfactant with a bulky headgroup containing eight pH-responsive groups. The hypothesis was that the amphoteric nature of the chelating surfactant would affect the interaction with another surfactant and, consequently, also the composition of mixed surface layers. Binary mixed monolayers of C12-DTPA and the anionic surfactant sodium dodecyl sulfate (SDS) were examined using neutron reflection and surface tension measurements. The experiments were conducted at pH 5, where the C12-DTPA monomers carried a net negative charge. Surface excess calculations at low total surfactant concentration revealed that the chelating surfactant dominated the surface composition. However, as the concentration was raised, the surface composition shifted toward an SDS-dominant state. This phenomenon was attributed to the increased ionic strength at increased concentrations, which altered the balance between competing entropic forces in the system. Interaction parameters for mixed monolayer formation were calculated, following a framework based on regular solution theory. In accordance with the hypothesis, the chelating surfactant's ability to modulate its charge and mitigate repulsive interactions in the surface layer resulted in favorable interactions between the anionic SDS and negatively charged C12-DTPA monomers. These interactions were found to be concentration-dependent, which was consistent with the observed shift in the surface layer composition.
A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under "near-equilibrium" conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling "defect" patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly "defective" film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications.
The kinetics and morphology of the ordering of block copolymer (BCP) films are highly dependent on the processing pathway, as the enthalpic and entropic forces driving the ordering processes can be quite different depending on process history. We may gain some understanding and control of this variability of BCP morphology with processing history through a consideration of the free energy landscape of the BCP material and a consideration of how the processing procedure moves the system through this energy landscape in a way that avoids having the system becoming trapped into well-defined metastable minima having a higher free energy than the target low free energy ordered structure. It is well known that standard thermal annealing (TA) of BCPs leads to structures corresponding to a well-defined stable free energy minimum; however, the BCP must be annealed for a very long time before the target low free energy structures can be achieved. Herein, we show that the same target low-energy structure can be achieved relatively quickly by subjecting as-cast films to an initial solvent annealing [direct immersion annealing (DIA) or solvent vapor annealing (SVA)] procedure, followed by a short period of TA. This process relies on lowering the activation energy barrier by reducing the glass-transition temperature through DIA (or SVA), followed by a multi-interface chain rearrangement through sequential TA. This energy landscape approach to ordering should be applicable to the process design for ordering many other complex materials.
While the phase separation of binary mixtures of chemically different polymer-grafted nanoparticles (PGNPs) is observed to superficially resemble conventional polymer blends, the presence of a "soft" polymer-grafted layer on the inorganic core of these nanoparticles qualitatively alters the phase separation kinetics of these "nanoblends" from the typical pattern of behavior seen in polymer blends and other simple fluids. We investigate this system using a direct immersion annealing method (DIA) that allows for a facile tuning of the PGNPs phase boundary, phase separation kinetics, and the ultimate scale of phase separation after a sufficient "aging" time. In particular, by switching the DIA solvent composition from a selective one (which increases the interaction parameter according to Timmerman's rule) to an overall good solvent for both PGNP components, we can achieve rapid switchability between phase-separated and homogeneous states. Despite a relatively low and non-classical power-law coarsening exponent, the overall phase separation process is completed on a time scale on the order of a few minutes. Moreover, the roughness of the PGNP blend film saturates at a scale that is proportional to the in-plane phase separation pattern scale, as observed in previous blend and block copolymer film studies. The relatively low magnitude of the coarsening exponent n is attributed to a suppression of hydrodynamic interactions between the PGNPs. The DIA method provides a significant opportunity to control the phase separation morphology of PGNP blends by solution processing, and this method is expected to be quite useful in creating advanced materials.
The surface adsorption of bovine serum albumin in pure water and salted aqueous solutions was studied by neutron reflection. With the contrast match technique, the surface excess in null reflecting water as a function of the protein concentration was revealed. It is found that, in a concentration range from 1 ppm (parts per million, mg/L) to 1000 ppm, without salts, the surface excess shows a profound peak at around 20 ppm; with salts, the surface excess increases steadily with the protein concentration. When the surface excess at a specific protein concentration is viewed, the introduction of sodium chloride causes either a salting down effect (surface adsorption decline) or a salting up effect (surface adsorption increase), depending upon the protein concentration. The salting up effect is observed at the low (â¼1 ppm) and high (â¼1000 ppm) concentrations, and the salting down effect dominates the intermediate concentration range. The change in solution pH relative to the isoelectric point (PI) can act as a simple indicator for the salting up or salting down behavior. When the solution pH is shifted toward the PI by adding salts, surface adsorption enhances; when the solution pH is shifted away from the PI by adding salts, surface adsorption declines.
Sodium Chloride , Water , Adsorption , Salts , Serum Albumin, Bovine
Collagen is a skeleton of native extracellular matrix (ECM) that is known to provide mechanical and structural stability. In an attempt to develop a new connective cellular model with the surrounding ECM without further experimental complications, such as the reconstitution of ECM receptors, we designed the experiments and discovered that the fibrillogenesis of membrane-bound collagen is not spontaneous as it is in the form of free collagen in bulk solution. The confocal microscopic results suggest that cholesterol is a crucial component that facilitates the fibril formation on the membrane surface. In situ X-ray and neutron reflectivity on Langmuir monolayer and solid-supported lipid bilayer models, respectively, reveal two features of cholesterol effects on the collagen fibril formation. Mainly, cholesterol increases the lateral lipid headgroup separation on the membrane surface, which promotes the association degree of collagen monomers. It also enhances the elastic modulus of the membrane to impede membrane filtration by the collagen assemblies.
Collagen , Extracellular Matrix , Cholesterol , Cytoskeleton , Elastic Modulus
Maintaining the integrity of cell membranes is indispensable for cellular viability. Poloxamer 188 (P188), a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer with a number-average molecular weight of 8700 g/mol and containing 80% by mass PEO, protects cell membranes from various external injuries and has the potential to be used as a therapeutic agent in diverse applications. The membrane protection mechanism associated with P188 is intimately connected with how this block copolymer interacts with the lipid bilayer, the main component of a cell membrane. Here, we report the distribution of P188 in a model lipid bilayer comprising 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) using neutron reflectivity (NR) and atomic force microscopy (AFM). We also investigated the association of a PEO homopolymer (PEO8.4K; Mn = 8400 g/mol) that does not protect living cell membranes. These experiments were conducted following incubation of a 4.5 mmol/L polymer solution in a buffer that mimics physiological conditions with supported POPC bilayer membranes followed by washing with the aqueous medium. In contrast to previous reports, which dealt with P188 and PEO in salt-free solutions, both P188 and PEO8.4K penetrate into the inner portion of the lipid bilayer as revealed by NR, with approximately 30% by volume occupancy across the membrane without loss of bilayer structural integrity. These results indicate that PEO is the chemical moiety that principally drives P188 binding to bilayer membranes. No defects or phase-separated domains were observed in either P188- or PEO8.4K-incubated lipid bilayers when examined by AFM, indicating that polymer chains mingle homogeneously with lipid molecules in the bilayer. Remarkably, the breakthrough force required for penetration of the AFM tip through the bilayer membrane is unaffected by the presence of the large amount of P188 and PEO8.4K.
Lipid Bilayers , Propylene Glycols , Polyethylene Glycols , Polymers
Styrene-maleic acid (SMA) copolymers have recently gained attention for their ability to facilitate the detergent-free solubilization of membrane protein complexes and their native boundary lipids into polymer-encapsulated, nanosized lipid particles, referred to as SMALPs. However, the interfacial interactions between SMA and lipids, which dictate the mechanism, efficiency, and selectivity of lipid and membrane protein extraction, are barely understood. Our recent finding has shown that SMA 1440, a chemical derivative of the SMA family with a functionalized butoxyethanol group, was most active in galactolipid-rich membranes, as opposed to phospholipid membranes. In the present work, we have performed X-ray reflectometry (XRR) and neutron reflectometry (NR) on the lipid monolayers at the liquid-air interface followed by the SMA copolymer adsorption. XRR and Langmuir Π-A isotherms captured the fluidifying effect of galactolipids, which allowed SMA copolymers to infiltrate easily into the lipid membranes. NR results revealed the detailed structural arrangement of SMA 1440 copolymers within the membranes and highlighted the partition of butoxyethanol group into the lipid tail region. This work allows us to propose a possible mechanism for the membrane solubilization by SMA.
For polymer-blend films, local dynamics in confined polymer domains tend to differ from the bulk because of significant contributions from the polymer-polymer interface. Herein, we investigated the diffusion dynamics of entangled polymer thin films confined between different polymers in a direction perpendicular to the surface using neutron reflectivity. We found that a bilayer of poly(methyl methacrylate) (PMMA) and deuterated PMMA (dPMMA) sandwiched between polystyrene (PS) layers exhibited significant increase in mobility near the polymer-polymer interface with decreasing PMMA thickness. This indicates that the contribution of repulsive interactions at the immiscible polymer-polymer interface becomes more significant as the film thickness decreases. We also found that the interfacial roughness between PMMA and PS (28 Å at equilibrium) and soft confinement of PS layers did not significantly affect the change in the diffusion dynamics of the adjacent PMMA. This was evidenced by comparison with the diffusion results of multilayers with a flat interface (8 Å at equilibrium) between PMMA and hard PS by UV cross-linking.
The morphological structure and dynamics of confined polymers adjacent to the polymer-polymer interface have a profound effect on determining the overall physical properties of polymer blends. We measured the diffusion dynamics of poly(methyl methacrylate) (PMMA) melts confined between polystyrene (PS) layers using neutron reflectivity. Combinations of various thicknesses of PMMA and deuterated PMMA (dPMMA) allowed us to experimentally reveal the nonmonotonic behavior of polymer mobility near the PS-PMMA interface. From the neutron reflectivity results, we found that the polymers adjacent to the immiscible polymer-polymer interface showed enhanced diffusion dynamics because of the repulsive interaction between PS and PMMA, whereas the polymer at local regions farther from the interface exhibited reduced dynamics. This is probably due to the nonspherical conformation of PMMA and spatial confinement near the PS-PMMA interface.
We investigated the effect of the morphological structure of a graphene oxide (GO) monolayer on the dewetting dynamics of the upper polymer thin films. The Langmuir-Schaefer (LS) technique was used to prepare a wrinkled GO ( wrGO) structure with a root mean square (rms) roughness of 22.7 Å. The dewetting behavior of poly(methyl methacrylate) (PMMA) thin films on the wrGO monolayers was perfectly prevented, whereas the PMMA thin films on a flat GO monolayer were dewetted at 203 °C. This wrinkle effect of the GO can be also obtained when the GOs monolayers are intercalated to the PMMA/polystyrene (PS) interface. In this multilayer, the flat GO monolayer at the interface between the PS and PMMA layers was spontaneously roughened with rms roughness of 46.9 Å after annealing and also prohibited the dewetting behavior. From the results, we found that to improve the compatibility of polymer blends by adding the two-dimensional nanosheets, it is important to control the morphological structure of the sheets at the interface, along with manipulation of the GO-polymer interactions.
We present a simple and facile approach to creating asymmetrically modified graphene oxide sheets by grafting polymers with different polarities. Single-layered Janus graphene derivatives were prepared by grafting polymers with different polarities at the liquid-gas interface through one step functionalization. This approach allows obtaining free-standing monolayers of Janus graphene oxide sheets for large area, and also controlling the morphology (i.e., wrinkled Janus graphene oxide sheets) by a compression monolayer. A neutron reflectivity technique is used to check the functionalization on each side of the monolayer, and the results are compared with contact angles to determine its amphiphilic nature. The free-standing Janus monolayers become robust after UV-irradiation, and are able to withstand various solvents. Because these robust Janus graphene films can maintain their anisotropic functionalities over time, this technique provides a new strategy for fabricating functional materials that require amphiphilic properties (i.e., oil-water separation membranes and chemical compatibilizers functioning as a 2D surfactant) and different electrical functionalities (i.e., flexible lightweight p-n junction semiconductors and stimuli-driven actuators).
We demonstrate that hybrid structures of graphene and single-walled carbon nanotubes (SWNTs) are precisely controlled at the liquid-gas interface. The functionalized SWNT Langmuir monolayers anchor single-layer graphene nanosheets (GNSs) suspended in water via Coulomb interaction at the interface. This GNS/SWNT hybrid multilayer electrode can be a promising anode material for Li-ion batteries, offering high specific capacity, outstanding power capability, and excellent cyclability.
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.
Lipid Bilayers/metabolism , Viral Envelope Proteins/metabolism , Virus Internalization , Amino Acid Sequence , Animals , Cells, Cultured , Hydrogen Bonding , Lipid Bilayers/chemistry , Membrane Fusion , Models, Molecular , Molecular Dynamics Simulation , Neutrons , Protein Binding , Spodoptera , Viral Envelope Proteins/chemistry , Virus Attachment
Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.
We have studied an orientation structure of self-assembled block copolymers (dPS-b-PMMA) of deuterated polystyrene (dPS) and poly(methyl methacrylate) (PMMA) confined between graphene oxide (GO) surfaces. The results of combination techniques, such as neutron reflectivity, time-of-flight secondary-ion mass spectrometry, grazing-incidence small-angle X-ray scattering, and scanning electron microscopy, show that self-assembled domains of the block copolymers in thin films near the GO sheets are oriented perpendicular to the surface of the GO monolayers, in contrast to the horizontal lamellar structure of the copolymer thin film in the absence of the GO monolayers. This is due to the amphiphilic nature of the GO, which leads to a nonpreferential interaction of both dPS and PMMA blocks. Double-sided confinement with the GO monolayers further extends the ordering behavior of the dPS-b-PMMA thin films. Continuous vertical orientation of the block copolymer thin films is also obtained in the presence of alternating GO layers within thick copolymer films.
We present a method for the direct measurement of the relative energy of interaction between a solvated polymer and a solid interface. By tethering linear chains covalently to the surface, we ensured the idealized and constant configuration of polymer molecules for measurement, modeling, and parameter estimation. For the case of amine-terminated polystyrene bound to a glycidoxypropyl silane film submerged in cyclohexane-d12, we estimated the χ parameter for the temperature range 10.7 °C to 52.0 °C, and found a downward sloping trend that crosses the χ = 0.5 threshold at 37 °C to 40 °C, in agreement with solution estimates for the same system. We simultaneously estimated the surface interaction parameter χs at each temperature, finding a decreasing affinity of the chains for the surface with increasing temperature, consistent with empirical observations. The theoretical model shows some limitations in a stronger solvent (toluene-d8) that prevent rigorous parameter estimation, but we demonstrate a qualitative change in χ and χs towards stronger solvency and weaker surface interaction with increasing temperature.
We report that the addition of a non-photoactive tertiary polymer phase in the binary bulk heterojunction (BHJ) polymer solar cell leads to a self-assembled columnar nanostructure, enhancing the charge mobilities and photovoltaic efficiency with surprisingly increased optimal active blend thicknesses over 300 nm, 3-4 times larger than that of the binary counterpart. Using the prototypical poly(3-hexylthiophene) (P3HT):fullerene blend as a model BHJ system, we discover that the inert poly(methyl methacrylate) (PMMA) added in the binary BHJ blend self-assembles into vertical columns, which not only template the phase segregation of electron acceptor fullerenes but also induce the out-of-plane rotation of the edge-on-orientated crystalline P3HT phase. Using complementary interrogation methods including neutron reflectivity, X-ray scattering, atomic force microscopy, transmission electron microscopy, and molecular dynamics simulations, we show that the enhanced charge transport originates from the more randomized molecular stacking of the P3HT phase and the spontaneous segregation of fullerenes at the P3HT/PMMA interface, driven by the high surface tension between the two polymeric components. The results demonstrate a potential method for increasing the thicknesses of high-performance polymer BHJ solar cells with improved photovoltaic efficiency, alleviating the burden of stringently controlling the ultrathin blend thickness during the roll-to-roll-type large-area manufacturing environment.
Neutron and X-ray reflection measurements have been used to study the structure of the adsorbed layer of a chelating surfactant at the air/liquid interface. The chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) has a large headgroup containing eight donor atoms that can participate in the coordination of metal ions. The donor atoms are also titrating, resulting in an amphoteric surfactant that can adopt a number of differently charged species depending on the pH. Very strong coordination complexes are formed with metal ions, where the metal ion can be considered as part of the surfactant structure, in contrast to monovalent cations that act as regular counterions to the negative net charge. Adsorption was investigated over a large concentration interval, from well below the critical micelle concentration (cmc) to five times the cmc. The most striking result is the maximum in the surface excess found around the cmc, which is consistent with previous indications from surface tension measurements. Adding divalent metal ions has a limited effect on the adsorption at the air/liquid interface. The reason is the coordination of the metal ion, resulting in compensating deprotonation of the complex. Small variations in the headgroup area of different metal complexes are found, correlating to the conditional stability constants. Adding sodium chloride has a significant effect on the adsorption behavior, and the results indicate that the protonation equilibrium is more important than the ionic strength effects. From combined fits of the neutron and X-ray data, a model that consists of a thick headgroup region and a relatively thin dehydrated tail region is found, and it indicates that the tails are not fully extended and that the limiting area per molecule is determined by the bulky headgroup.
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.
