ConspectusIn principle, the incorporation of guest nanoparticles within host crystals should provide a straightforward and versatile route to a wide range of nanocomposite materials. However, ...crystallization normally involves expelling impurities, so nanoparticle occlusion is both counter-intuitive and technically challenging. Clearly, the nanoparticles should have a strong interaction with the growing crystalline lattice, but quantifying such an affinity has been challenging; the basic principles that govern efficient nanoparticle occlusion within inorganic single crystals are rather poorly understood. In the past few years, we have focused on the elucidation of robust design rules for such systems; our progress is summarized in this article.Polymerization-induced self-assembly (PISA) is widely recognized as a powerful platform technology for the preparation of a broad range of model organic nanoparticles. Herein, PISA was exploited to prepare sterically stabilized diblock copolymer nano-objects (e.g., spheres, worms, or vesicles) of varying size using steric stabilizers of well-defined chain length, variable anionic charge density, tunable surface density, and adjustable chemical functionality (e.g., carboxylic acid, phosphate, sulfate or sulfonate groups). Thus, we were able to systematically investigate how such structural parameters influence nanoparticle occlusion. Given its commercial importance for many industrial sectors, calcium carbonate was selected as the model host crystal for nanoparticle occlusion studies. Perhaps surprisingly, the extent of nanoparticle occlusion is not particularly sensitive to nanoparticle size or morphology. However, the steric stabilizer chain length can play a key role: relatively short chains lead to surface-confined occlusion, while sufficiently long chains enable uniform nanoparticle occlusion to be achieved throughout the crystal lattice (albeit sometimes inducing a significant change in crystal morphology). Optimizing the anionic charge density and surface density of the stabilizer chains is required to maximize the extent of nanoparticle occlusion, while steric stabilizer chains comprising anionic carboxylate groups led to greater occlusion compared to those composed of phosphate, sulfate, or sulfonate groups when examining a model vesicle system.Subsequently, our occlusion studies were extended to include functional hybrid nanocomposite crystals. For example, the spatially controlled occlusion of poly(glycerol monomethacrylate)-stabilized gold nanoparticles was achieved within semiconductive ZnO crystals by either controlling the nanoparticle concentration or by delaying their addition to the reaction mixture. Moreover, oil droplets of up to 500 nm have been incorporated into calcite crystals at up to 11% by mass, despite the large mismatch in surface energy between the hydrophobic oil droplets and the ionic crystal lattice. We have also explored a "Trojan horse" strategy, whereby cargos comprising nanoparticles or soluble dye molecules are first encapsulated within anionic block copolymer vesicles prior to their incorporation within calcite crystals. This approach offers a generic and efficient strategy for the occlusion of many types of guest species into single crystals. In summary, we have established important guidelines for efficient nanoparticle occlusion within crystals, which opens up new avenues for the synthesis of next-generation hybrid materials.
Recent advances in polymer science are enabling substantial progress in nanobiotechnology, particularly in the design of new tools for enhanced understanding of cell biology and for smart drug ...delivery formulations. Herein, a range of novel galactosylated diblock copolymer nano-objects is prepared directly in concentrated aqueous solution via reversible addition–fragmentation chain transfer polymerization using polymerization-induced self-assembly. The resulting nanospheres, worm-like micelles, or vesicles interact in vitro with galectins as judged by a turbidity assay. In addition, galactosylated vesicles are highly biocompatible and allow intracellular delivery of an encapsulated molecular cargo.
The very low sliding friction at natural synovial joints, which have friction coefficients of μ < 0.002 at pressures up to 5 megapascals or more, has to date not been attained in any human-made ...joints or between model surfaces in aqueous environments. We found that surfaces in water bearing polyzwitterionic brushes that were polymerized directly from the surface can have μ values as low as 0.0004 at pressures as high as 7.5 megapascals. This extreme lubrication is attributed primarily to the strong hydration of the phosphorylcholine-like monomers that make up the robustly attached brushes, and may have relevance to a wide range of human-made aqueous lubrication situations.
Various carboxylic acid-functionalized poly( N , N -dimethylacrylamide) (PDMAC) macromolecular chain transfer agents (macro-CTAs) were chain-extended with diacetone acrylamide (DAAM) by reversible ...addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization at 70 °C and 20% w/w solids to produce a series of PDMAC–PDAAM diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). TEM studies indicate that a PDMAC macro-CTA with a mean degree of polymerization (DP) of 68 or higher results in the formation of well-defined spherical nanoparticles with mean diameters ranging from 40 to 150 nm. In contrast, either highly anisotropic worms or polydisperse vesicles are formed when relatively short macro-CTAs (DP = 40–58) are used. A phase diagram was constructed to enable accurate targeting of pure copolymer morphologies. Dynamic light scattering (DLS) and aqueous electrophoresis studies indicated that in most cases these PDMAC–PDAAM nano-objects are surprisingly resistant to changes in either solution pH or temperature. However, PDMAC40–PDAAM99 worms do undergo partial dissociation to form a mixture of relatively short worms and spheres on adjusting the solution pH from pH 2–3 to around pH 9 at 20 °C. Moreover, a change in copolymer morphology from worms to a mixture of short worms and vesicles was observed by DLS and TEM on heating this worm dispersion to 50 °C. Postpolymerization cross-linking of concentrated aqueous dispersions of PDMAC–PDAAM spheres, worms, or vesicles was performed at ambient temperature using adipic acid dihydrazide (ADH), which reacts with the hydrophobic ketone-functionalized PDAAM chains. The formation of hydrazone groups was monitored by FT-IR spectroscopy and afforded covalently stabilized nano-objects that remained intact on exposure to methanol, which is a good solvent for both blocks. Rheological studies indicated that the cross-linked worms formed a stronger gel compared to linear precursor worms.
In this Perspective, we summarize recent progress in polymerization-induced self-assembly (PISA) for the rational synthesis of block copolymer nanoparticles with various morphologies. Much of the ...PISA literature has been based on thermally initiated reversible addition–fragmentation chain transfer (RAFT) polymerization. Herein, we pay particular attention to alternative PISA protocols, which allow the preparation of nanoparticles with improved control over copolymer morphology and functionality. For example, initiation based on visible light, redox chemistry, or enzymes enables the incorporation of sensitive monomers and fragile biomolecules into block copolymer nanoparticles. Furthermore, PISA syntheses and postfunctionalization of the resulting nanoparticles (e.g., cross-linking) can be conducted sequentially without intermediate purification by using various external stimuli. Finally, PISA formulations have been optimized via high-throughput polymerization and recently evaluated within flow reactors for facile scale-up syntheses.
Poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) diblock copolymer vesicles can be prepared in the form of concentrated aqueous dispersions via polymerization-induced ...self-assembly (PISA). In the present study, these syntheses are conducted in the presence of varying amounts of silica nanoparticles of approximately 18 nm diameter. This approach leads to encapsulation of up to hundreds of silica nanoparticles per vesicle. Silica has high electron contrast compared to the copolymer which facilitates TEM analysis, and its thermal stability enables quantification of the loading efficiency via thermogravimetric analysis. Encapsulation efficiencies can be calculated using disk centrifuge photosedimentometry, since the vesicle density increases at higher silica loadings while the mean vesicle diameter remains essentially unchanged. Small angle X-ray scattering (SAXS) is used to confirm silica encapsulation, since a structure factor is observed at q ≈ 0.25 nm–1. A new two-population model provides satisfactory data fits to the SAXS patterns and allows the mean silica volume fraction within the vesicles to be determined. Finally, the thermoresponsive nature of the diblock copolymer vesicles enables thermally triggered release of the encapsulated silica nanoparticles simply by cooling to 0–10 °C, which induces a morphological transition. These silica-loaded vesicles constitute a useful model system for understanding the encapsulation of globular proteins, enzymes, or antibodies for potential biomedical applications. They may also serve as an active payload for self-healing hydrogels or repair of biological tissue. Finally, we also encapsulate a model globular protein, bovine serum albumin, and calculate its loading efficiency using fluorescence spectroscopy.
We report the first example of a non-aqueous Pickering nanoemulsion, which comprises glycerol droplets dispersed in mineral oil. The droplet phase is stabilized by hydrophobic sterically stabilized ...poly(lauryl methacrylate)-poly(benzyl methacrylate) nanoparticles which are prepared directly in mineral oil using polymerization-induced self-assembly. First, a glycerol-in-mineral oil Pickering macroemulsion with a mean droplet diameter of 2.1 ± 0.9 μm is prepared via high-shear homogenization using excess nanoparticles as an emulsifier. Then, this precursor macroemulsion is subjected to high-pressure microfluidization (a single pass at an applied pressure of 20,000 psi) to produce glycerol droplets of approximately 200–250 nm diameter. Transmission electron microscopy studies indicate preservation of the distinctive superstructure produced by nanoparticle adsorption at the glycerol/mineral oil interface, thus confirming the Pickering nature of the nanoemulsion. Glycerol is sparingly soluble in mineral oil, thus such nanoemulsions are rather susceptible to destabilization via Ostwald ripening. Indeed, substantial droplet growth occurs within 24 h at 20 °C, as judged by dynamic light scattering. However, this problem can be suppressed by dissolving a non-volatile solute (sodium iodide) in glycerol prior to formation of the nanoemulsion. This reduces diffusional loss of glycerol molecules from the droplets, with analytical centrifugation studies indicating much better long-term stability for such Pickering nanoemulsions (up to 21 weeks). Finally, the addition of just 5% water to the glycerol phase prior to emulsification enables the refractive index of the droplet phase to be matched to that of the continuous phase, leading to relatively transparent nanoemulsions.
Display omitted
Colloidosomes represent a rapidly expanding field with various applications in microencapsulation, including the triggered release of cargoes. With self-assembled shells comprising ...colloidal particles, they offer significant flexibility with respect to microcapsule functionality. This review explores the various types of particles and techniques that have been employed to prepare colloidosomes. The relative advantages and disadvantages of these routes are highlighted and their potential as microcapsules for both small molecule and macromolecular actives is evaluated.
Reversible addition–fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on ...poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC25–PHPMA400 particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16–25% solids in aqueous solution.
It is well‐known that the self‐assembly of AB diblock copolymers in solution can produce various morphologies depending on the relative volume fraction of each block. Recently, polymerization‐induced ...self‐assembly (PISA) has become widely recognized as a powerful platform technology for the rational design and efficient synthesis of a wide range of block copolymer nano‐objects. In this study, PISA is used to prepare a new thermoresponsive poly(N‐(2‐hydroxypropyl) methacrylamide)‐poly(2‐hydroxypropyl methacrylate) PHPMAC‐PHPMA diblock copolymer. Remarkably, TEM, rheology and SAXS studies indicate that a single copolymer composition can form well‐defined spheres (4 °C), worms (22 °C) or vesicles (50 °C) in aqueous solution. Given that the two monomer repeat units have almost identical chemical structures, this system is particularly well‐suited to theoretical analysis. Self‐consistent mean field theory suggests this rich self‐assembly behavior is the result of the greater degree of hydration of the PHPMA block at lower temperature, which is in agreement with variable temperature 1H NMR studies.
Every which way and loose: A single amphiphilic thermoresponsive diblock copolymer can reversibly form spheres, worms or vesicles in aqueous solution. Self‐consistent mean field theory indicates that this rich self‐assembly behavior arises from the temperature‐dependent degree of hydration of the structure‐directing hydrophobic poly(2‐hydroxypropyl methacrylate) block.
PDF
