Amphiphilic Films Research Articles

New amphiphilic block copolymer-modified electrodes for supercapacitors

Herein, amphiphilic block copolymer-modified film electrodes were fabricated using poly(acrylic acid)-b-poly(acrylonitrile)-b-poly(acrylic acid) as a surface modifier, polyethersulfone as a matrix polymer, and activated carbon as an active substance by the phase separation method to enhance the wettability of the electrodes.

Conformation mediated preferential swelling of amphiphilic block copolymer ultrathin films

Steady-state and dynamic swelling characteristics of PEO-PPO-PEO copolymer ultrathin films comprising 2-layered structure, where the bottom layer (L1) is made of one PEO (hydrophilic)-PPO (hydrophobic) bilayer and the top layer (L2) is made of two alternating PEO-PPO bilayers, have been studied at room temperature in precisely controlled environment of 10–93% relative humidity (RH). Swelling, which is monitored by measuring the thickness of the films using X-ray reflectivity (XRR), is found to be largely dissimilar in differently thick films prepared by varying the concentration of mother solutions from 1 g/L to 4 g/L. This is well explained considering a preferential-swelling of amphiphilic block copolymer, where only the hydrophilic PEO blocks contribute in swelling and PPO acts a barrier in the diffusion of water molecules. The swelling kinetics is governed by the thickness/width and coverage of outer PPO block layer.

Film Confinement Induced "Jump-Percolation" Wetting Transition in Amphiphilic Block Copolymer Films.

We report a first-order like sharp surface wettability transition with varying film thickness dependent morphology in cast films of an amphiphilic triblock copolymer. Films composed of poly(2-(N-ethylperfluorooctanesulfonamido) ethyl methyl acrylate), poly(FOSM), and poly(N,N'-dimethyl acrylamide), poly(DMA), with thickness (h) in the transition-range, 200 < h < 300 nm, exhibited an abrupt hydrophobic to hydrophilic dynamic water contact angle transition. After an induction time, ti ≈ 40 to 180 s, water contact angle varied as θc ≈ 116° to 40° with an ultrafast contact angle decay time constant, [Formula: see text] ≈ -18°/s. This behavior is a result of competing heterogeneous and antagonistic effects of bumpy poly(DMA) wetting domains against a nonwetting planar poly(FOSM) background, with a "jump percolation" wetting transition when the poly(DMA) domain density reaches unity. Outside of this film thickness range, relatively shallow decreasing water contact angle gradients were observed with a monotonically increasing poly(DMA) domain area coverage with increasing film thickness in the overall range of 40 nm (hydrophobic, θc ≈ 118°) < h < 500 nm (hydrophilic, θc ≈ 8°). The optical diffuse reflectance properties of these rough surfaces exhibit an onset of diffuse reflectance maxima correlated to the transition morphology film thickness.

Supramolecular Host-Guest Interaction-Enhanced Adjustable Drug Release Based on β-Cyclodextrin-Functionalized Thermoresponsive Porous Polymer Films.

Drug delivery systems based on stimuli-responsive porous polymer films (PPFs) have been extensively investigated because of their many advantages. However, the ability to adjust the drug release from PPFs is not always perfect, and at times, it cannot satisfy real-world requirements. In this paper, supramolecular host-guest interactions were harnessed to overcome the difficulties associated with adjustable release from these systems by incorporating host molecules into the pore walls of thermoresponsive PPFs. β-Cyclodextrin-functionalized porous amphiphilic block copolymer films (β-CD-PBCPFs) with controllable pore parameters, high homogeneity, and large areas were prepared by combining the self-assembly and breath-figure methods. Drug-loaded β-CD-PBCPFs displayed thermoresponsive release behavior, which could be tuned by increasing the β-CD content in phosphate-buffered saline. The release was governed by the host-guest interactions of the β-CD moieties and drug molecules. The concept of host-guest interaction-enhanced adjustable release could be applied to different drug molecules, such as doxorubicin and metronidazole.

Carbohydrate-Based Block Copolymer Thin Films: Ultrafast Nano-Organization with 7 nm Resolution Using Microwave Energy.

Block copolymers (BCP) can self-assemble into nanoscale patterns with a wide variety of applications in the semiconductor industry. The self-assembly of BCPs is commonly accomplished by solvent vapor or thermal annealing, but generally these methods require long time (few hours) to obtain nanostructured thin films. In this contribution, a new and ultrafast method (using microwaves) is proposed-high temperature solvent vapor annealing (HTSVA), combining solvent vapor annealing with thermal annealing, to achieve fast and controllable self-assembly of amphiphilic BCP thin films. A promising carbohydrate-based BCP capable of forming cylindrical patterns with some of the smallest feature sizes is used for demonstrating how to obtain a highly ordered vertical cylindrical pattern with sub-10 nm feature sizes in few seconds by HTSVA. HTSVA provides not only a simple way to achieve BCP fast self-assembly in practical applications but also a tool to study the self-assembly behavior of BCPs under extreme conditions.

A Dendritic Amphiphile for Efficient Control of Biomimetic Calcium Phosphate Mineralization.

The phase behavior of a dendritic amphiphile containing a Newkome-type dendron as the hydrophilic moiety and a cholesterol unit as the hydrophobic segment is investigated at the air-liquid interface. The amphiphile forms stable monomolecular films at the air-liquid interface on different subphases. Furthermore, the mineralization of calcium phosphate beneath the monolayer at different calcium and phosphate concentrations versus mineralization time shows that at low calcium and phosphate concentrations needles form, whereas flakes and spheres dominate at higher concentrations. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron diffraction confirm the formation of calcium phosphate. High-resolution transmission electron microscopy and electron diffraction confirm the predominant formation of octacalcium phosphate and hydroxyapatite. The data also indicate that the final products form via a complex multistep reaction, including an association step, where nano-needles aggregate into larger flake-like objects.

Influence of the amphiphilicity profile of copolymers on the formation of liquid crystalline mesophases in microemulsions

In bicontinuous microemulsions, the increase of the solubilization capacity of a surfactant, e.g., by the addition of amphiphilic block copolymers (“boosting effect”), is normally accompanied by the formation of liquid crystalline mesophases. We studied a new class of amphiphilic polymers as “boosters,” so-called gradient polymers, with a gradual change from the hydrophilic to the hydrophobic part. Phase diagram measurements and static and quasielastic neutron scattering experiments reveal that the polymers cause a stiffening of the amphiphilic film while simultaneously the saddle splay modulus decreases such that the formation of liquid crystalline mesophases, normally present with diblock polymers as “boosters,” is suppressed, while bicontinuous structures are geometrically favored. In addition, these findings are supported by theoretical calculations following the works of Lipowsky. Hence, gradient amphiphilic polymers not only increase the efficiency of surfactants but simultaneously suppress the formation of liquid crystalline phases thereby greatly increasing their application potential.

Supramolecular chirality of amphiphilic block copolymer films made through two steps: self-assembling first, and then solution coating.

Supramolecular chirality is achieved in amphiphilic block copolymer films made through two-step fabrication: self-assembling first and then solution coating. The amphiphilic block copolymer is composed of poly(N-isopropyl acrylamide) (pNIPAM) as hydrophilic segments and poly(methyl methacrylate) with chiral side groups as hydrophobic segments. The films fabricated by two steps show sensible circular dichroism (CD) signals around a wavelength of 200 nm. However, CD signals cannot be detected from films made by directly coating the solution of copolymers on the quartz surface. The CD signal at about 200 nm is from supramolecular arrangement of benzene units connected to the chiral group in the hydrophobic segment. This result is thought to be originated from the aggregation of the copolymer during the first step of the film forming process, and the corresponding investigation into factors affecting this process has been performed in this work. It is also found that the films fabricated by two steps can adsorb chiral small molecules enantioselectively, while the films obtained by coating the solution of copolymers directly have no such enatioselective adsorption ability.

Kinetic and electrical phenomena in gas–liquid systems

Disperse systems consisting of a liquid and gas bubbles located in it are considered. Two possible versions of evolution of bubbles under the conditions studied are assessed. In simple liquids, contact between two bubbles causes them to merge, as the separating film breaks. In the case of complex organic liquids, amphiphilic film is formed on the surface of bubbles, and the lifetime of bubbles in contact increases with their size. Under an external electric field, chains of bubbles are formed, lined up along the electric field potential lines. The presence of bubbles in liquid greatly lowers the breakdown threshold, as the critical parameters of the breakdown field in liquids are two to three orders of magnitude higher than those in gases at atmospheric pressure. Various breakdown mechanisms in liquids are discussed from the viewpoint of formation of the gas phase during the passage of an electric current through a liquid medium. The character of propagating a streamer in separate bubbles is studied with their random distribution in liquid and in the case of formation of some structures of bubbles; the critical parameters of disperse systems, that can lead to their electrical breakdown, are presented. Along with the general concepts of electrical breakdown in dispersed systems, experimental studies of these processes are considered, and the nature of electrical breakdown in liquid dielectrics, including transformer oil, is discussed.

Marine fungi as source of new hydrophobins

Hydrophobins have been described as the most powerful surface-active proteins known. They are produced by filamentous fungi and exhibit a distinct amphiphilic structure determining their self-assembly at hydrophilic-hydrophobic interfaces and surfactant properties which have been demonstrated to be useful for several biotechnological applications. The marine environment represents a vast natural resource of new molecules produced by organisms growing in various stressful conditions. This study was focused on the screening of 100 marine fungi from Mycoteca Universitatis Taurinensis (MUT) for the identification of new hydrophobins. Four different methods were set up to extract hydrophobins of class I and II, from the mycelium or the culture broth of fungi. Six fungi were selected as the best producers of hydrophobins endowed with different characteristics. Their ability to form stable amphiphilic films and their emulsification capacity in the presence of olive oil was evaluated.

Hydration-Induced Phase Transitions in Surfactant and Lipid Films.

For several surfactant and lipid systems, it is crucial to understand how hydration influences the physical and chemical properties. When humidity changes, it affects the degree of hydration by adding or removing water molecules. In many cases, this process induces transitions between liquid crystalline phases. This phenomenon is of general interest for numerous applications simply because of the fact that humidity variations are ubiquitous. Of particular interest are hydration-induced phase transitions in amphiphilic films, which in many cases appear as the frontier toward a vapor phase with changing humidity. Considering this, it is important to characterize the film thickness needed for the formation of 3D liquid crystalline phases and the lyotropic phase behavior of this kind of film. In this work, we study this issue by employing a recently developed method based on the humidity scanning quartz crystal microbalance with dissipation monitoring (HS QCM-D), which enables continuous scanning of the film hydration. We investigate five surfactants films (DDAO, DTAC, CTAC, SDS, and n-octylβ-d-glucoside) and one lipid film (monoolein) and show that HS QCM-D enables the fast characterization of hydration-induced phase transitions with small samples. Film thicknesses range from tens to hundreds of nanometers, and clear phase transitions are observed in all cases. It is shown that phase transitions in films occur at the same water activities as for corresponding bulk samples. This allows us to conclude that surfactant and lipid films, with a thickness of as low as 50 nm, are in fact assembled as 3D-structured liquid crystalline phases. Furthermore, liquid crystalline phases of surfactant films show liquidlike behavior, which decreases the accuracy of the absorbed water mass measurement. On the other hand, the monoolein lipid forms more rigid liquid crystalline films, allowing for an accurate determination of the water sorption isotherm, which is also true for the sorption isotherms corresponding to the solid surfactant phases.

A journey through the phase diagram of a pharmaceutically relevant microemulsion system

HypothesisThe phase behavior and the properties of water, oil, surfactant, and cosurfactant mixtures depend on the fine balance of different forces, among them the bending energy of the amphiphilic film. Thus, it should be possible to control the structural evolution of nonionic microemulsions by the cosurfactant content and the hydration of the surfactant headgroup. ExperimentsAn extensive investigation of the pseudoternary phase diagram of mixtures of water, isopropyl palmitate, polyoxyethylene (10) oleyl ether Brij 97 (C18E10), and butanol is presented for two different cosurfactant concentrations, thereby varying the hydrophilicity of the amphiphile. The studies were performed employing conductometric titrations, differential scanning calorimetry (DSC), and small-angle neutron scattering (SANS). FindingsA systematic growth of the domain sizes and correlation lengths is observed by increasing the water content in the initial oil/surfactant solution. The formation of a bicontinuous structure, as deduced from conductivity is directly related to the presence of free water unbound to the EO units of the surfactant, as determined by DSC. The experimental results, e.g., the extension of the different phase regions and the mesoscopic structure are discussed on a molecular level, therefore providing a direct link between the composition of the microemulsions and the resulting structure and properties.

Spin-Casting Polymer Brush Films for Stimuli-Responsive and Anti-Fouling Surfaces.

Surfaces modified with amphiphilic polymers can dynamically alter their physicochemical properties in response to changes of their environmental conditions; meanwhile, amphiphilic polymer coatings with molecular hydrophilic and hydrophobic patches, which can mitigate biofouling effectively, are being actively explored as advanced coatings for antifouling materials. Herein, a series of well-defined amphiphilic asymmetric polymer brushes containing hetero side chains, hydrophobic polystyrene (PS) and hydrophilic poly(ethylene glycol) (PEG), was employed to prepare uniform thin films by spin-casting. The properties of these films were investigated by water contact angle, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and quartz crystal microbalance (QCM). AFM showed smooth surfaces for all films with the roughness less than 2 nm. The changes in water contact angle and C/O ratio (XPS) evidenced the enrichment of PEG or PS chains at film surface after exposed to selective solvents, indicative of stimuli- responsiveness. The adsorption of proteins on PEG functionalized surface was quantified by QCM and the results verified that amphiphilic polymer brush films bearing PEG chains could lower or eliminate protein-material interactions and resist to protein adsorption. Cell adhesion experiments were performed by using HaCaT cells and it was found that polymer brush films possess good antifouling ability.

Exploring Nonspecific Protein Adsorption on Lignocellulosic Amphiphilic Bicomponent Films

In this contribution, we explore the interaction of lignocellulosics and proteins aiming at a better understanding of their synergistic role in natural systems. In particular, the manufacturing and characterization of amphiphilic bicomponent thin films composed of hydrophilic cellulose and a hydrophobic lignin ester in different ratios is presented which may act as a very simplified model for real systems. Besides detailed characterizations of the films and mechanisms to explain their formation, nonspecific protein adsorption using bovine serum albumin (BSA) onto the films was studied using a quartz crystal microbalance with dissipation (QCM-D). As it turns out, the rather low nonspecific protein adsorption of BSA on cellulose is further reduced when these hydrophobic lignins are incorporated into the films. The lignin ester acts in these blend films as sacrificial component, probably via an emulsification mechanism. Additionally, the amphiphilicity of the films may prevent the adsorption of BSA as well. Although there are some indications, it remains unclear whether any kind of protein interactions in such systems are of specific nature.

Class I Hydrophobin Vmh2 Adopts Atypical Mechanisms to Self-Assemble into Functional Amyloid Fibrils.

Hydrophobins are fungal proteins whose functions are mainly based on their capability to self-assemble into amphiphilic films at hydrophobic-hydrophilic interfaces (HHI). It is widely accepted that class I hydrophobins form amyloid-like structures, named rodlets, which are hundreds of nanometers long, packed into ordered lateral assemblies and do not exhibit an overall helical structure. We studied the self-assembly of the Class I hydrophobin Vmh2 from Pleurotus ostreatus in aqueous solutions by dynamic light scattering (DLS), thioflavin T (ThT), fluorescence assay, circular dichroism (CD), cryogenic trasmission electron microscopy (cryo-TEM), and TEM. Vmh2 does not form fibrillar aggregates at HHI. It exhibits spherical and fibrillar assemblies whose ratio depends on the protein concentration when freshly solubilized at pH ≥ 7. Moreover, it spontaneously self-assembles into isolated, micrometer long, and twisted amyloid fibrils, observed for the first time in fungal hydrophobins. This process is promoted by acidic pH, temperature, and Ca(2+) ions. A model of self-assembly into amyloid-like structures has been proposed.

In vitro degradation behavior of functionalized cellulosic fibers reinforced PLA composite

Event Abstract Back to Event In vitro degradation behavior of functionalized cellulosic fibers reinforced PLA composite M.reza Foruzanmehr1, Mathieu R. Robert1, Pascal Vuillaume2 and Said Elkoun1 1 Universite de Sherbrooke, Carrefour of Innovative Technologies and Ecodesign, Canada 2 Centre de Technologie Minérale et de Plasturgie, Canada Cellulosic fibers are renewable and also light in weight which make them a good candidate as reinforcing elements in bio-composites. Having hydrophilic nature resulted by presence of hydroxyl groups in the structure of these fibers restricts their application in the polymeric matrices because of poor interfacial adhesion, and the low dispersion within the matrix. To resolve these problems this study tried firstly to functionalize the flax fibers with selective oxidation. This improves the adhesion of subsequent amphiphilic TiO2 thin films created by Sol-Gel technique. The PLA matrices were reinforced by using non/functionalized, TiO2/ non –coated flax fibers. The composites were conditioned in simulated body solution at 37°C to induce the degradation. The behaviour of the PLA/glass composite has been analysed during its degradation in simulated physiological condition. Physical and mechanical properties of the composites and the interfacial strength between the matrix and the fibers were characterized quantitatively and qualitatively. The results showed better interfacial properties within functionalized flax fiber reinforced composites comparing to non-functionalized ones. Functionalized TiO2 coated flax reinforced composites showed better mechanical properties within the first 15 weeks of conditioning comparing to the control samples.

Solvent free synthesis and structural evaluation of polyurethane films based on poly(ethylene glycol) and poly(caprolactone)

Biodegradable amphiphilic polyurethane films (bio-PUs) were synthesized by solvent free polyaddition reaction of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(caprolactone) (PCL) as macrodiols with hexamethylene diisocyanate. Samples were subsequently heat cured in order to obtain 3D crosslinked structure. Different PCL/PEG ratios allowed controlling the toughness of the resulting bio-PUs. Significant enhancement of Young's modulus, strength and elongation at break was observed at a PCL/PEG molar ratio above 3. The change in the bio-PU mechanical behavior was ascribed to the formation of crystalline PCL domains in the bio-PU network. The presence of PEG increased both the ability to absorb water and the rate of hydrolytic degradation, while PCL increased the cell viability. Prepared solvent free bio-PUs may advantageously be used in medicine as elastic resorbable material applicable against post-surgical adhesions.

Alcohol as tuning parameter in an IL-containing microemulsion: The quaternary system EAN –n- octane–C 12 E 3 –1-octanol

Abstract With an appropriate tuning parameter a microemulsion can be forced to undergo a phase inversion, i.e. to invert the curvature of the amphiphilic film. In microemulsions consisting of water, an n -alkane and a nonionic alkyl polyglycolether (C i E j ) temperature is an appropriate parameter since the surfactant head groups dehydrate with increasing temperature. Recently we were able to show that this also holds true for ethylammonium nitrate (EAN)– n -alkane–C i E j systems. However, the temperature sensitivity is weaker which is why we decided to use a hydrophobic cosurfactant to induce a phase inversion in the EAN-containing microemulsion. We studied the quaternary system EAN– n -octane–C 12 E 3 − 1-octanol as a function of the alcohol concentration at T = 15 °C and found the same trends as for the aqueous counterparts. (1) Studying the phase behavior as a function of the alcohol content ( δ ) and of the total surfactant concentration ( γ ), one finds that the phase boundaries resemble the shape of a fish. (2) Measuring the interfacial tension σ between the IL- and oil-rich phase, one observes a minimum in the center of the three-phase region. (3) NMR self-diffusion measurements reveal a transition from an oil-in-EAN microemulsion to a bicontinuous microemulsion and finally to an EAN-in-oil microemulsion.

Stereocomplex Film Using Triblock Copolymers of Polylactide and Poly(ethylene glycol) Retain Paxlitaxel on Substrates by an Aqueous Inkjet System.

The stereocomplex formation of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA) using an inkjet system was expanded to the amphiphilic copolymers, using poly(ethylene glycol) (PEG) as a hydrophilic polymer. The diblock copolymers, which are composed of PEG and PLLA (MPEG-co-PLLA) and PEG and PDLA (MPEG-co-PDLA), were employed for thin-film preparation using an aqueous inkjet system. The solvent and temperature conditions were optimized for the stereocomplex formation between MPEG-co-PLLA and MPEG-co- PDLA. As a result, the stereocomplex was adequately formed in acetonitrile/water (1:1, v/v) at 40 °C. The aqueous conditions improved the stereocomplex film preparation, which have suffered from clogging when using the organic solvents in previous work. The triblock copolymers, PLLA-co-PEG-co-PLLA and PDLA-co-PEG-co-PDLA, were employed for square patterning with the inkjet system, which produced thin films. The amphiphilic polymer film was able to retain hydrophobic compounds inside. The present result contributed to the rapid film preparation by inkjet, retaining drugs with difficult solubility in water, such as paclitaxel within the films.

On‐the‐Spot Immobilization of Quantum Dots, Graphene Oxide, and Proteins via Hydrophobins

Class I hydrophobin Vmh2, a peculiar surface active and versatile fungal protein, is known to self‐assemble into chemically stable amphiphilic films, to be able to change wettability of surfaces, and to strongly adsorb other proteins. Herein, a fast, highly homogeneous and efficient glass functionalization by spontaneous self‐assembling of Vmh2 at liquid–solid interfaces is achieved (in 2 min). The Vmh2‐coated glass slides are proven to immobilize not only proteins but also nanomaterials such as graphene oxide (GO) and quantum dots (QDs). As models, bovine serum albumin labeled with Alexa 555 fluorophore, anti‐immunoglobulin G antibodies, and cadmium telluride QDs are patterned in a microarray fashion in order to demonstrate functionality, reproducibility, and versatility of the proposed substrate. Additionally, a GO layer is effectively and homogeneously self‐assembled onto the studied functionalized surface. This approach offers a quick and simple alternative to immobilize nanomaterials and proteins, which is appealing for new bioanalytical and nanobioenabled applications.