Tracking Sulfonated Polystyrene Diffusion in a Chitosan/Carboxymethyl Cellulose Layer-by-Layer Film: Exploring the Internal Architecture of Nanocoatings.

Since chitosan presents the ability to interact with a wide range of molecules, it has been one of the most popular natural polymers for the construction of layer-by-layer thin films. In this study, depth-profiling X-ray photoelectron spectroscopy (XPS) was employed to track the diffusion of sulfonated polystyrene (SPS) in carboxymethyl cellulose/chitosan (CMC/Chi) multilayers. Our findings suggest that the CMC/Chi film does not constitute an electrostatic barrier sufficient to block diffusion of SPS, and that diffusion can be controlled by adjusting the diffusion time and the molecular weight of the polymers that compose the CMC/Chi system. In addition to monitoring the diffusion, it was also possible to observe a process of preferential interaction between Chi and SPS. Thus, the nitrogen N 1s peak, due to functional groups found exclusively in chitosan chains, was the key factor to identifying the molecular interactions involving chitosan and the different polyanions. Accordingly, the presence of a strong polyanion such as SPS shifts the N 1s peak to a higher level of binding energy. Such results highlight that understanding the fundamentals of polymer interactions is a major step to fine-tuning the internal architecture of LbL structures for specific applications (e.g., drug release).

Reversible Self-Healing for Preserving Optical Transparency and Repairing Mechanical Damage in Composites.

This research concentrates on the healing of optical properties, roughness, contact angle hysteresis, and shallow scratches in polymer/nanoparticle composites. A series of ternary composite blends [epoxy/halloysite nanotubes (HNTs)/cellulose acetate butyrate (CAB)] with various CAB concentrations were fabricated and subjected to a series of mechanical damages. The optimized concentration of a nanoparticle is 1.0 vol %, and the CAB concentration is 3.0 vol % based on the mechanical reinforcement and wear resistance. Nanoscale scratching, microlevel falling-sand test, and macrolevel Taber abrasions were utilized to damage the surfaces. The induced damage (roughness and surface scratch up to hundreds of nanometers in depth) healed upon heating. At any temperatures above the softening transition of the semi-interpenetrating network structure of the polymer composites, CAB migrates into the microcracks, and the essential mechanical parameters (modulus, strength, strain to failure) are recovered; in our particular epoxy/HNTs/CAB system, optical transparency is also recovered efficiently. CAB also moves to the macroscopic air/specimen interface and favorably modifies the surface properties, reducing the roll-off angles of water droplets from ∼90° to ∼20°. Through an appropriate choice of CAB additives with different molecular weights, the healing temperature can be tailored.

Investigation of the Internal Chemical Composition of Chitosan-Based LbL Films by Depth-Profiling X-ray Photoelectron Spectroscopy (XPS) Analysis.

Chitosan-based thin films were assembled using the layer-by-layer technique, and the axial composition was accessed using X-ray photoelectron spectroscopy with depth profiling. Chitosan (CHI) samples possessing different degrees of acetylation ([Formula: see text]) and molecular weight ([Formula: see text]) produced via the ultrasound-assisted deacetylation reaction were used in this study along with two different polyanions, namely, sodium polystyrenesulfonate (PSS) and carboxymethylcellulose (CMC). When chitosan, a positively charged polymer in aqueous acid medium, was combined with a strong polyanion (PSS), the total positive charge of chitosan, directly related to its [Formula: see text], was the key factor affecting the film formation. However, for CMC/CHI films, the pH of the medium and [Formula: see text] of chitosan strongly affected the film structure and composition. Consequently, the structure and the axial composition of chitosan-based films can be finely adjusted by choosing the polyanion and defining the chitosan to be used according to its DA and [Formula: see text] for the desired application, as demonstrated by the antibacterial tests.

Macrophages with cellular backpacks for targeted drug delivery to the brain.

Most potent therapeutics are unable to cross the blood-brain barrier following systemic administration, which necessitates the development of unconventional, clinically applicable drug delivery systems. With the given challenges, biologically active vehicles are crucial to accomplishing this task. We now report a new method for drug delivery that utilizes living cells as vehicles for drug carriage across the blood brain barrier. Cellular backpacks, 7-10 µm diameter polymer patches of a few hundred nanometers in thickness, are a potentially interesting approach, because they can act as drug depots that travel with the cell-carrier, without being phagocytized. Backpacks loaded with a potent antioxidant, catalase, were attached to autologous macrophages and systemically administered into mice with brain inflammation. Using inflammatory response cells enabled targeted drug transport to the inflamed brain. Furthermore, catalase-loaded backpacks demonstrated potent therapeutic effects deactivating free radicals released by activated microglia in vitro. This approach for drug carriage and release can accelerate the development of new drug formulations for all the neurodegenerative disorders.

Superoleophilic Titania Nanoparticle Coatings with Fast Fingerprint Decomposition and High Transparency.

Low surface tension sebaceous liquids such as human fingerprint oils are readily deposited on high energy surfaces such as clean glass, leaving smudges that significantly lower transparency. There have been several attempts to prevent formation of these dactylograms on glass by employing oil-repellent textured surfaces. However, nanotextured superoleophobic coatings typically scatter visible light, and the intrinsic thermodynamic metastability of the composite superoleophobic state can result in failure of the oil repellency under moderate contact pressure. We develop titania-based porous nanoparticle coatings that are superoleophilic and highly transparent and which exhibit short time scales for decomposition of fingerprint oils under ultraviolet light. The mechanism by which a typical dactylogram is consumed combines wicking of the sebum into the nanoporous titania structure followed by photocatalytic degradation. We envision a wide range of applications because these TiO2 nanostructured surfaces remain photocatalytically active against fingerprint oils in natural sunlight and are also compatible with flexible glass substrates.

Enhanced Wear Resistance of Transparent Epoxy Composite Coatings with Vertically Aligned Halloysite Nanotubes.

The influence of nanoparticle orientation on wear resistance of transparent composite coatings has been studied. Using a nozzle spray coating method, halloysite nanotubes (HNTs) were aligned in the in-plane and out-of-plane directions and in various randomly oriented states. Nanoscratching, falling sand, and Taber Abrasion tests were used to characterize the wear resistance at different length scales. Composites consistently displayed better wear resistance than pure epoxy. Samples with out-of-plane particle orientations exhibited better wear-resistant behavior than those with in-plane particle distributions. In nanoscratching tests, the out-of-plane orientation decreases the normalized scratch volume by as much as 60% compared to pure epoxy. In the falling sand and Taber Abrasion tests, out-of-plane aligned halloysite particles resulted in surfaces with smaller roughness based on stylus profilometry and SEM observations. The decrease in roughness values after these wear tests can be as large as 67% from pure epoxy to composites. Composites with higher out-of-plane particle orientation factors exhibited better light transmittance after sand impingements and other wear tests. This study suggests a useful strategy for producing material systems with enhanced mechanical durability and more durable optical properties.

Spray-Coated Halloysite-Epoxy Composites: A Means To Create Mechanically Robust, Vertically Aligned Nanotube Composites.

Halloysite nanotube-filled epoxy composites were fabricated using spray-coating methods. The halloysite nanotubes (HNTs) were aligned by the hydrodynamic flow conditions at the spray nozzle, and the polymer viscosity helped to preserve this preferential orientation in the final coatings on the target substrates. Electron microscopy demonstrated a consistent trend of higher orientation degree in the nanocomposite coatings as viscosity increased. The nanoindentation mechanical performances of these coatings were studied using a Hysitron TriboIndenter device. Composites showed improvements up to ∼50% in modulus and ∼100% in hardness as compared to pure epoxy, and the largest improvements in mechanical performance correlated with higher alignment of HNTs along the plane-normal direction. Achieving this nanotube alignment using a simple spray-coating method suggests potential for large-scale production of multifunctional anisotropic nanocomposite coatings on a variety of rigid and deformable substrates.

Liposome-Loaded Cell Backpacks.

Cell backpacks, or micron-scale patches of a few hundred nanometers in thickness fabricated by layer-by-layer (LbL) assembly, are potentially useful vehicles for targeted drug delivery on the cellular level. In this work, echogenic liposomes (ELIPs) containing the anticancer drug doxorubicin (DOX) are embedded into backpacks through electrostatic interactions and LbL assembly. Poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA)n , and poly(diallyldimethylammonium chloride)/poly(styrene sulfonate) (PDAC/SPS)n film systems show the greatest ELIP incorporation of the films studied while maintaining the structural integrity of the vesicles. The use of ELIPs for drug encapsulation into backpacks facilitates up to three times greater DOX loading compared to backpacks without ELIPs. Cytotoxicity studies reveal that monocyte backpack conjugates remain viable even after 72 h, demonstrating promise as drug delivery vehicles. Because artificial vesicles can load many different types of drugs, ELIP containing backpacks offer a unique versatility for broadening the range of possible applications for cell backpacks.

Optimization of amine-rich multilayer thin films for the capture and quantification of prostate-specific antigen.

It is demonstrated that poly(allylamine hydrochloride)/poly(styrenesulfonate) (PAH/SPS) multilayer films can be successfully tailored for the capture and detection of small biomolecules in dilute concentrations. Based on in vitro results, these films could be potentially applied for rapid and high-throughput diagnosis of dilute biomarkers in serum or tissue. PAH presents functional amino groups that can be further reacted with desired chemistries in order to create customizable and specific surfaces for biomolecule capture. A variety of film assembly characteristics were tested (pH, molecular weight of PAH, and ionic strength) to tune the biotinylation and swelling behavior of these films to maximize detection capabilities. The resultant optimized biotinylated PAH/SPS 9.3/9.3 system was utilized in conjunction with quantum dots (Qdots) to capture and detect a dilute biomarker for prostate cancer, prostate-specific antigen (PSA). Compared to previous work, our system presents a good sensitivity for PSA detection within the clinically relevant range of 0.4-100 ng/mL.

Tuning the properties of mucin via layer-by-layer assembly.

Multilayer films consisting of bovine submaxillary mucin (BSM) and poly(allylamine hydrochloride) (PAH) were prepared on various substrates using layer-by-layer assembly. The effects of both the assembly pH and ionic strength on multilayer characteristics were investigated by assessing film thicknesses (10-80 nm), surface wetting characteristics, and cell repulsion. Also, the dynamic assembly behavior was monitored using quartz crystal microbalance with dissipation monitoring (QCM-D) to further understand the effect of assembly pH on film characteristics. Assembly studies revealed that substantial amounts of BSM adhere to the outermost surface only at low pH conditions. The resulting multilayer films assembled at low pH conditions were found to exhibit hydrophilic and cell repellent behavior. In addition, it was found that batch-to-batch variations of the biopolymer BSM could dramatically alter properties.

Monocyte-mediated delivery of polymeric backpacks to inflamed tissues: a generalized strategy to deliver drugs to treat inflammation.

Targeted delivery of drugs and imaging agents to inflamed tissues, as in the cases of cancer, Alzheimer's disease, Parkinson's disease, and arthritis, represents one of the major challenges in drug delivery. Monocytes possess a unique ability to target and penetrate into sites of inflammation. Here, we describe a broad approach to take advantage of the natural ability of monocytes to target and deliver flat polymeric particles ("Cellular Backpacks") to inflamed tissues. Cellular backpacks attach strongly to the surface of monocytes but do not undergo phagocytosis due to backpack's size, disk-like shape and flexibility. Following attachment of backpacks, monocytes retain important cellular functions including transmigration through an endothelial monolayer and differentiation into macrophages. In two separate in vivo inflammation models, backpack-laden monocytes exhibit increased targeting to inflamed tissues. Cellular backpacks, and their abilities to attach to monocytes without impairing monocyte functions and 'hitchhike' to a variety of inflamed tissues, offer a new platform for both cell-mediated therapies and broad targeting of inflamed tissues.

Determination of lithium-ion distributions in nanostructured block polymer electrolyte thin films by X-ray photoelectron spectroscopy depth profiling.

X-ray photoelectron spectroscopy (XPS) depth profiling with C60(+) sputtering was used to resolve the lithium-ion distribution in the nanometer-scale domain structures of block polymer electrolyte thin films. The electrolytes of interest are mixtures of lithium trifluoromethanesulfonate and lamellar-forming polystyrene-poly(oligo(oxyethylene)methacrylate) (PS-POEM) copolymer. XPS depth profiling results showed that the lithium-ion concentration was directly correlated with the POEM concentration. Furthermore, chemical state and atomic composition of the film were analyzed through the deconvolution of the C1s signal, indicating that the lithium ions appear to be uniformly distributed in the POEM domains. Overall, the unique capabilities of C60(+) depth profiling XPS provide a powerful tool for the analysis of nanostructured polymer thin films in applications ranging from energy storage and generation to surface coatings and nanoscale templates.

Design and fabrication of zwitter-wettable nanostructured films.

Manipulating surface properties using chemistry and roughness has led to the development of advanced multifunctional surfaces. Here, in a nanostructured polymer film consisting of a hydrophilic reservoir of chitosan/carboxymethyl cellulose capped with various hydrophobic layers, we demonstrate the role of a third design factor, water permeation rate. We use this additional design criterion to produce antifogging coatings that readily absorb water vapor while simultaneously exhibiting hydrophobic character to liquid water. These zwitter-wettable films, produced via aqueous layer-by-layer assembly, consist of a nanoscale thin hydrophobic capping layer (chitosan/Nafion) that enables water vapor to diffuse rapidly into the underlying hydrophilic reservoir rather than nucleating drops of liquid water on the surface. We characterize these novel films using a quartz crystal microbalance with dissipation monitoring (QCM-D) and via depth-profiling X-ray photoelectron spectroscopy (XPS) in addition to extensive testing for fogging/antifogging performance.

Sugar-mediated disassembly of mucin/lectin multilayers and their use as pH-Tolerant, on-demand sacrificial layers.

The layer-by-layer (LbL) assembly of thin films on surfaces has proven to be an extremely useful technology for uses ranging from optics to biomedical applications. Releasing these films from the substrate to generate so-called free-standing multilayer films opens a new set of applications. Current approaches to generating such materials are limited because they can be cytotoxic, difficult to scale up, or have undesirable side reactions on the material. In this work, a new sacrificial thin film system capable of chemically triggered dissolution at physiological pH of 7.4 is described. The film was created through LbL assembly of bovine submaxillary mucin (BSM) and the lectin jacalin (JAC) for a (BSM/JAC) multilayer system, which remains stable over a wide pH range (pH 3-9) and at high ionic strength (up to 5 M NaCl). This stability allows for subsequent LbL assembly of additional films in a variety of conditions, which could be released from the substrate by incubation in the presence of a competitive inhibitor sugar, melibiose, which selectively disassembles the (BSM/JAC) section of the film. This novel multilayer system was then applied to generate free-standing, 7 µm diameter, circular ultrathin films, which can be attached to a cell surface as a "backpack". A critical thickness of about 100 nm for the (BSM/JAC) film was required to release the backpacks from the glass substrate, after incubation in melibiose solution at 37 °C for 1 h. Upon their release, backpacks were subsequently attached to murine monocytes without cytotoxicity, thereby demonstrating the compatibility of this mucin-based release system with living cells.

Quantification of feather structure, wettability and resistance to liquid penetration.

Birds in the cormorant (Phalacrocoracidae) family dive tens of metres into water to prey on fish while entraining a thin layer of air (a plastron film) within the microstructures of their feathers. In addition, many species within the family spread their wings for long periods of time upon emerging from water. To investigate whether wetting and wing-spreading are related to feather structure, microscopy and photographic studies have previously been used to extract structural parameters for barbs and barbules. In this work, we describe a systematic methodology to characterize the quasi-hierarchical topography of bird feathers that is based on contact angle measurements using a set of polar and non-polar probing liquids. Contact angle measurements on dip-coated feathers of six aquatic bird species (including three from the Phalacrocoracidae family) are used to extract two distinguishing structural parameters, a dimensionless spacing ratio of the barbule (D*) and a characteristic length scale corresponding to the spacing of defect sites. The dimensionless spacing parameter can be used in conjunction with a model for the surface topography to enable us to predict a priori the apparent contact angles of water droplets on feathers as well as the water breakthrough pressure required for the disruption of the plastron on the feather barbules. The predicted values of breakthrough depths in water (1-4 m) are towards the lower end of typical diving depths for the aquatic bird species examined here, and therefore a representative feather is expected to be fully wetted in a typical deep dive. However, thermodynamic surface energy analysis based on a simple one-dimensional cylindrical model of the feathers using parameters extracted from the goniometric analysis reveals that for water droplets on feathers of all six species under consideration, the non-wetting 'Cassie-Baxter' composite state represents the global energy minimum of the system. By contrast, for other wetting liquids, such as alkanes and common oils, the global energy minimum corresponds to a fully wetted or Wenzel state. For diving birds, individual feathers therefore spontaneously dewet once the bird emerges out of water, and the 'wing-spreading' posture might assist in overcoming kinetic barriers associated with pinning of liquid droplets that retard the rate of drying of the wet plumage of diving birds.

Orientation-specific attachment of polymeric microtubes on cell surfaces.

Tubular particles presenting heterogeneous regions of chemistry on the tube-ends versus the side are fabricated and are shown to control the particle orientation on the surface of live lymphocytes. Controlling the orientation of anisotropic microparticles on cell surfaces is of interest for biomedical applications and drug delivery in particular, since it can be used to promote or resist particle internalization.

Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers.

Functional organic thin films often demand precise control over the nanometer-level structure. Interlayer diffusion of materials may destroy this precise structure; therefore, a better understanding of when interlayer diffusion occurs and how to control it is needed. X-ray photoelectron spectroscopy paired with C60(+) cluster ion sputtering enables high-resolution analysis of the atomic composition and chemical state of organic thin films with depth. Using this technique, we explore issues common to the polyelectrolyte multilayer field, such as the competition between hydrogen bonding and electrostatic interactions in multilayers, blocking interlayer diffusion of polymers, the exchange of film components with a surrounding solution, and the extent and kinetics of interlayer diffusion. The diffusion coefficient of chitosan (M = ∼100 kDa) in swollen hydrogen-bonded poly(ethylene oxide)/poly(acrylic acid) multilayer films was examined and determined to be 1.4*10(-12) cm(2)/s. Using the high-resolution data, we show that upon chitosan diffusion into the hydrogen-bonded region, poly(ethylene oxide) is displaced from the film. Under the conditions tested, a single layer of poly(allylamine hydrochloride) completely stops chitosan diffusion. We expect our results to enhance the understanding of how to control polyelectrolyte multilayer structure, what chemical compositional changes occur with diffusion, and under what conditions polymers in the film exchange with the solution.

Zwitter-wettability and antifogging coatings with frost-resisting capabilities.

Antifogging coatings with hydrophilic or even superhydrophilic wetting behavior have received significant attention due to their ability to reduce light scattering by film-like condensation. However, under aggressive fogging conditions, these surfaces may exhibit frost formation or excess and nonuniform water condensation, which results in poor optical performance of the coating. In this paper, we show that a zwitter-wettable surface, a surface that has the ability to rapidly absorb molecular water from the environment while simultaneously appearing hydrophobic when probed with water droplets, can be prepared by using hydrogen-bonding-assisted layer-by-layer (LbL) assembly of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). An additional step of functionalizing the nano-blended PVA/PAA multilayer with poly(ethylene glycol methyl ether) (PEG) segments produced a significantly enhanced antifog and frost-resistant behavior. The addition of the PEG segments was needed to further increase the nonfreezing water capacity of the multilayer film. The desirable high-optical quality of these thin films arises from the nanoscale control of the macromolecular complexation process that is afforded by the LbL processing scheme. An experimental protocol that not only allows for the exploration of a variety of aggressive antifogging challenges but also enables quantitative analysis of the antifogging performance via real-time monitoring of transmission levels as well as image distortion is also described.

pH-Programmable Sequential Dissolution of Multilayer Stacks of Hydrogen-Bonded Polymers.

We report that the interlayer diffusion of polymer chains within heterostructured hydrogen-bonded multilayer films depends on the stacking order: polymers diffuse more when high pH stability polymer pairs are assembled on top of low pH stability polymer pairs. By varying the stacking sequence, the fraction of the film that is released from the substrate can be tuned to achieve sequential pH-programmed release of the multilayer film. Also, we show that a multifunctional freestanding film with tunable film thickness can be generated by appropriate stacking and subsequent thermal cross-linking.

Templated nanopores for robust functional surface porosity in poly(methyl methacrylate).

A novel "sink and etch" technique is used to generate stable surface nanoporosity in poly(methyl methacrylate). Layer-by-layer assembly is first used to conformally coat PMMA substrates with a uniform layer of silica nanoparticles. Thermal annealing is then applied to cause sinking and engulfment of the silica nanoparticles into the thermoplastic PMMA surface. By selectively etching away the layer of embedded silica nanoparticles, a conformal porous layer of inversely templated structure can be obtained in the PMMA surface. Characterization with atomic force microscopy shows that a variety of nanoporous surface morphologies can be achieved simply by controlling the duration and temperature of thermal annealing. The nanoporous surfaces consisting of either as assembled silica nanoparticles or templated inverse porosity in PMMA were compared in terms of their antireflective (AR) properties. Measuring AR properties provided a quantitative means to compare the stability of these porous AR surfaces before and after several cleaning cycles. Our results show that while both types of surface porosity can provide excellent AR properties (optimized for 300-400 nm), the porous layer generated by the "sink and etch" technique showed superior mechanical stability.