Fabrication of Polymer Ellipsoids by the Electrospinning of Swollen Nanoparticles

Electrospinning is used to deform originally spherical polymer nanoparticles into ellipsoidal nanoparticles. The polymer nanoparticles are swollen and the dispersion is then electrospun. Under certain conditions, the stretching generated in the electrospinning jet is enough to generate elongated nanoparticles embedded in fibers. The formation of the anisotropic particles is observed by stimulated emission depletion (STED) microscopy performed on fluorescent nanoparticles and by electron microscopy measurements on the nanoparticles recovered after removal of the fiber matrix

pH-Sensitive Polymer Conjugates for Anticorrosion and Corrosion Sensing

In 2015, the global cost of corrosion in the world was estimated to be around 2.5 trillion dollars and has been continuously increasing. The active protection by corrosion inhibitors is a well-known technique for protecting metals against corrosion. However, one major disadvantage is that corrosion inhibitors can be leached in the environment, even when corrosion does not occur. We design and synthesize smart polymer/corrosion inhibitor conjugates as a new generation of materials for corrosion protection. These materials release inhibitors upon acidification, which may occur either by acidic rain or as a consequence of the metal corrosion process itself. A polymerizable derivative of 8-hydroxyquinoline (8HQ), an effective corrosion inhibitor, is prepared so that it contains acid-labile β-thiopropionate linkages. The monomer is copolymerized with ethyl acrylate, and the obtained functional polymer is processed to form nanoparticles. Under acidic conditions, >95% 8HQ is released from the nanoparticles of the polymer conjugates after 14 days. However, the release was significantly slower under neutral conditions, reaching only 15% during the same period. Additionally, nonconjugated 8HQ can be physically entrapped in the nanoparticles of the polymer conjugates by encapsulation. The nonconjugated 8HQ is then released in less than 30 min so that the coexistence of both conjugated and nonconjugated 8HQ in the nanoparticles allows a release profile, which is a hybrid of sustained and burst releases. Furthermore, the nanoparticles are advantageously used as nanosensors. The 8HQ released from the nanoparticles displays enhanced fluorescence upon chelation with aluminum ions. Therefore, the nanoparticles can be used simultaneously for corrosion sensing and protection

Stimuli-Selective Delivery of two Payloads from Dual Responsive Nanocontainers

Stimuli-Selective Delivery of two Payloads from Dual Responsive Nanocontainer

Nanocontainers in and onto Nanofibers

ConspectusHierarchical structure is a key feature explaining the superior properties of many materials in nature. Fibers usually serve in textiles, for structural reinforcement, or as support for other materials, whereas spherical micro- and nanoobjects can be either highly functional or also used as fillers to reinforce structure materials. Combining nanocontainers with fibers in one single object has been used to increase the functionality of fibers, for example, antibacterial and thermoregulation, when the advantageous properties given by the encapsulated materials inside the containers are transferred to the fibers. Herein we focus our discussion on how the hierarchical structure composed of nanocontainers in nanofibers yields materials displaying advantages of both types of materials and sometimes synergetical effects. Such materials can be produced by first carefully designing nanocontainers with defined morphology and chemistry and subsequently electrospinning them to fabricate nanofibers. This method, called colloid-electrospinning, allows for marrying the properties of nanocontainers and nanofibers. The obtained fibers could be successfully applied in different fields such as catalysis, optics, energy conversion and production, and biomedicine.The miniemulsion process is a convenient approach for the encapsulation of hydrophobic or hydrophilic payloads in nanocontainers. These nanocontainers can be embedded in fibers by the colloid-electrospinning technique. The combination of nanocontainers with nanofibers by colloid-electrospinning has several advantages. (1) The fiber matrix serves as support for the embedded nanocontainers. For example, through combining catalysts nanoparticles with fiber networks, the catalysts can be easily separated from the reaction media and handled visually. This combination is beneficial for the reuse of the catalyst and the purification of products. (2) Electrospun nanofibers containing nanocontainers offer the active agents inside the nanocontainers a double protection by both the fiber matrix and the nanocontainers. Since the polymer of the fibers and the polymer of the nanocontainers have usually opposite polarities, the encapsulated substance, for example, catalysts, dyes, or drugs, can be protected against a large variety of environmental influences. (3) Electrospun nanofibers exhibit unique advantages for tissue engineering and drug delivery that are a structural similarity to the extracellular matrix of biological tissues, large specific surface area, high and interconnected porosity which enhances cell adhesion, proliferation, drug loading, and mass transfer properties, as well as the flexibility in selecting the raw materials. Moreover, the nanocontainer-in-nanofiber structure allows multidrug loading and programmable release of each drug, which are very important to achieve synergistic effects in tissue engineering and disease therapy.The advantages offered by these materials encourage us to further understand the relationship between colloidal properties and fibers, to predict the morphology and properties of the fibers obtained by colloid-electrospinning, and to explore new possible combination of properties offered by nanoparticles and nanofibers

Responsive Polymer-Layered Silicate Hybrids for Anticorrosion

Two-dimensional materials have been introduced in polymer coatings to increase the lifetime of metallic materials by providing barrier properties against corrosive species. Corrosion inhibitors can be inserted into a 2D filler to mitigate the corrosion of metallic materials caused by corrosive species. Current drawbacks of this approach include a poorly controlled release of the inhibitor and the incompatibility of the filler and polymer. To achieve long-term anticorrosion performance, a layered silicate (octosilicate) is modified by surface-graft polymerization with a monomer functionalized with a corrosion inhibitor, 8-hydroxyquinoline. A pH-responsive polymer-inhibitor conjugate, poly(methyl methacrylate-co-8-quinolinyl acrylate), is covalently attached to the silicate and then provides a sustainable release of the corrosion inhibitor upon acidification. The corrosion current density of aluminum alloy substrates (AA2024) coated with poly(methyl methacrylate-co-butyl acrylate) embedding the octosilicate containers is decreased due to a synergistic effect of barrier properties provided by the 2D filler and the pH-responsive release of corrosion inhibitor. This conceptual design can be potentially applied to release molecules such as drugs, fertilizers, or pesticides

Hydrophobic Nanocontainers for Stimulus-Selective Release in Aqueous Environments

The preparation of nanocontainers with a hydrophilic core from water-in-oil emulsions and their subsequent transfer to aqueous medium is crucial because it enables the efficient encapsulation of hydrophilic payloads in large quantities. However, major challenges are associated with their synthesis including low colloidal stability, leakage of encapsulated payloads due to osmotic pressure, and a demanding transfer of the nanocontainers from apolar to aqueous media. We present here a general approach for the synthesis of polymer nanocontainers that are colloidally stable, not sensitive to osmotic pressure, and responsive to environmental stimuli that trigger release of the nanocontainer contents. Additionally, the nanocontainers can selectively deliver one or two different payloads upon oxidation and changes of pH or temperature. Our approach uniquely enables the synthesis of nanocontainers for applications in which aqueous environments are desired or inevitable

Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water. By labeling the emulsion droplets with a copolymer of stearyl methacrylate and a polymerizable dye, we demonstrated that the migration of the monomer to the upper hexadecane layer relied on molecular diffusion rather than diffusion of monomer droplets to the oil layer. Moreover, surface tension measurements confirmed that the emulsions were still in the miniemulsion regime and not in the microemulsion regime. The particle size can be tuned by controlling the duration during which the miniemulsion stayed in contact with the hexadecane layer, the interfacial area between the miniemulsion and the hexadecane layer and by the concentration of surfactant. Our method was applied to reduce the size of polystyrene and poly(methyl methacrylate) nanoparticles, nanocapsules of a copolymer of styrene and methyl methacrylic acid, and silica nanocapsules. This work demonstrated that a successful reduction of nanoparticle size in the miniemulsion process can be achieved without using excess amounts of surfactant. The method relies on building osmotic pressure in oil droplets dispersed in water which acts as semipermeable membrane

Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water. By labeling the emulsion droplets with a copolymer of stearyl methacrylate and a polymerizable dye, we demonstrated that the migration of the monomer to the upper hexadecane layer relied on molecular diffusion rather than diffusion of monomer droplets to the oil layer. Moreover, surface tension measurements confirmed that the emulsions were still in the miniemulsion regime and not in the microemulsion regime. The particle size can be tuned by controlling the duration during which the miniemulsion stayed in contact with the hexadecane layer, the interfacial area between the miniemulsion and the hexadecane layer and by the concentration of surfactant. Our method was applied to reduce the size of polystyrene and poly(methyl methacrylate) nanoparticles, nanocapsules of a copolymer of styrene and methyl methacrylic acid, and silica nanocapsules. This work demonstrated that a successful reduction of nanoparticle size in the miniemulsion process can be achieved without using excess amounts of surfactant. The method relies on building osmotic pressure in oil droplets dispersed in water which acts as semipermeable membrane

Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water. By labeling the emulsion droplets with a copolymer of stearyl methacrylate and a polymerizable dye, we demonstrated that the migration of the monomer to the upper hexadecane layer relied on molecular diffusion rather than diffusion of monomer droplets to the oil layer. Moreover, surface tension measurements confirmed that the emulsions were still in the miniemulsion regime and not in the microemulsion regime. The particle size can be tuned by controlling the duration during which the miniemulsion stayed in contact with the hexadecane layer, the interfacial area between the miniemulsion and the hexadecane layer and by the concentration of surfactant. Our method was applied to reduce the size of polystyrene and poly(methyl methacrylate) nanoparticles, nanocapsules of a copolymer of styrene and methyl methacrylic acid, and silica nanocapsules. This work demonstrated that a successful reduction of nanoparticle size in the miniemulsion process can be achieved without using excess amounts of surfactant. The method relies on building osmotic pressure in oil droplets dispersed in water which acts as semipermeable membrane

Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water. By labeling the emulsion droplets with a copolymer of stearyl methacrylate and a polymerizable dye, we demonstrated that the migration of the monomer to the upper hexadecane layer relied on molecular diffusion rather than diffusion of monomer droplets to the oil layer. Moreover, surface tension measurements confirmed that the emulsions were still in the miniemulsion regime and not in the microemulsion regime. The particle size can be tuned by controlling the duration during which the miniemulsion stayed in contact with the hexadecane layer, the interfacial area between the miniemulsion and the hexadecane layer and by the concentration of surfactant. Our method was applied to reduce the size of polystyrene and poly(methyl methacrylate) nanoparticles, nanocapsules of a copolymer of styrene and methyl methacrylic acid, and silica nanocapsules. This work demonstrated that a successful reduction of nanoparticle size in the miniemulsion process can be achieved without using excess amounts of surfactant. The method relies on building osmotic pressure in oil droplets dispersed in water which acts as semipermeable membrane