Loading of silica nanoparticles in block copolymer vesicles during polymerization-induced self-assembly: encapsulation efficiency and thermally-triggered release

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 and its thermal stability enables quantification of the loading efficiency via thermogravimetric analysis. Encapsulation efficiencies can be obtained 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 thermo-responsive nature of the diblock copolymer enables thermally-triggered release of the encapsulated silica nanoparticles simply by cooling to 0-10 oC, which induces a morphological transition. These silica-loaded vesicles constitute a useful model system for understanding the encapsulation of globular proteins, enzymes or antibodies within block copolymer vesicles 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. Please click Additional Files below to see the full abstract

Shear-Induced Alignment of Block Copolymer Worms in Mineral Oil

Poly(stearyl methacrylate)-poly(benzyl methacrylate) [PSMA-PBzMA] diblock copolymer worms were synthesized directly in mineral oil via reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization at 90 °C. Free-standing gels were obtained from this polymerization-induced self-assembly (PISA) formulation when targeting PSMA13-PBzMA65 dispersions at 5% w/w to 20% w/w copolymer concentration. Gel permeation chromatography (GPC) studies indicated that almost identical copolymer chains were obtained in all cases, while transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies confirmed that highly anisotropic worms were formed with mean cross-sectional diameters of 11.9-13.1 nm. These worms undergo a thermoreversible worm-to-sphere transition on heating up to 150 °C. Rheological studies were conducted to characterize the shear rate- and concentration-dependent behaviour caused by this change in copolymer morphology, where the initial shear-thinning worm gels form spheres (i.e. a Newtonian fluid) on heating up to 150 °C. Complementary shear-induced polarized light imaging (SIPLI) experiments confirmed the formation of aligned linear worms under applied shear between 80 °C and 110 °C, with high-viscosity dispersions of branched worms being obtained at 20-60 °C and low-viscosity spheres being produced at 150 °C. This study informs the use of such block copolymer worms as rheology modifiers for non-polar oils, which is of potential interest for the automotive industry

Monodisperse macromolecules – A stepping stone to understanding industrial polymers

AbstractPolymers synthesized via anionic polymerization have proved important to our fundamental understanding of the processing, that is rheology and crystallisation, of bulk commodity polymers. The role of monodisperse hydrogenated polybutadienes as models for linear and branched polyethylene is examined. Systematic studies of the effects of long-chain branching, using well-defined “comb” materials have improved our understanding of how the number and length of branches affect the rheological properties and how these features impact on their crystallization behaviour. A combination of techniques including rheology, Small Angle X-ray Scattering (SAXS), and birefringence measurements have provided insight into role of linear long chains in the formation of oriented morphologies during the crystallization of hydrogenated polybutadiene blends of controlled polydispersity leading to the development of a quantitative model

Self-assembly-driven electrospinning:the transition from fibers to intact beaded morphologies

Polymer beads have attracted considerable interest for use in catalysis, drug delivery, and photo­nics due to their particular shape and surface morphology. Electrospinning, typically used for producing nanofibers, can also be used to fabricate polymer beads if the solution has a sufficiently low concentration. In this work, a novel approach for producing more uniform, intact beads is presented by electrospinning self-assembled block copolymer (BCP) solutions. This approach allows a relatively high polymer concentration to be used, yet with a low degree of entanglement between polymer chains due to microphase separation of the BCP in a selective solvent system. Herein, to demonstrate the technology, a well-studied polystyrene-poly(ethylene butylene)–polystyrene triblock copolymer is dissolved in a co-solvent system. The effect of solvent composition on the characteristics of the fibers and beads is intensively studied, and the mechanism of this fiber-to-bead is found to be dependent on microphase separation of the BCP

Time-Resolved SAXS Studies of the Kinetics of Thermally Triggered Release of Encapsulated Silica Nanoparticles from Block Copolymer Vesicles

Silica-loaded poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) diblock copolymer vesicles are prepared in the form of concentrated aqueous dispersions via polymerization-induced self-assembly (PISA). As the concentration of silica nanoparticles present during the PISA synthesis is increased up to 35% w/w, higher degrees of encapsulation of this component within the vesicles can be achieved. After centrifugal purification to remove excess non-encapsulated silica nanoparticles, SAXS, DCP, and TGA analysis indicates encapsulation of up to hundreds of silica nanoparticles per vesicle. In the present study, the thermally triggered release of these encapsulated silica nanoparticles is examined by cooling to 0 °C for 30 min, which causes in situ vesicle dissociation. Transmission electron microscopy studies confirm the change in diblock copolymer morphology and also enable direct visualization of the released silica nanoparticles. Time-resolved small-angle X-ray scattering is used to quantify the extent of silica release over time. For an initial silica concentration of 5% w/w, cooling induces a vesicle-to-sphere transition with subsequent nanoparticle release. For higher silica concentrations (20 or 30% w/w) cooling only leads to perforation of the vesicle membranes, but silica nanoparticles are nevertheless released through the pores. For vesicles prepared in the presence of 30% w/w silica, the purified silica-loaded vesicles were cooled to 0 °C for 30 min, and SAXS patterns were collected every 15 s. A new SAXS model has been developed to determine both the mean volume fraction of encapsulated silica within the vesicles and the scattering length density. Satisfactory data fits to the experimental SAXS patterns were obtained using this model

In situ small-angle X-ray scattering studies of sterically-stabilized diblock copolymer nanoparticles formed during polymerization-induced self-assembly in non-polar media

Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) is utilized to prepare a series of poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nano-objects at 90 °C directly in mineral oil. Polymerization-induced self-assembly (PISA) occurs under these conditions, with the resulting nanoparticles exhibiting spherical, worm-like or vesicular morphologies when using a relatively short PSMA13 macromolecular chain transfer agent (macro-CTA), as confirmed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. Only kinetically-trapped spherical nanoparticles are obtained when using longer macro-CTAs (e.g. PSMA18 or PSMA31), with higher mean degrees of polymerization (DPs) for the PBzMA core-forming block simply producing progressively larger spheres. SAXS is used for the first time to monitor the various morphological transitions that occur in situ during the RAFT dispersion polymerization of BzMA when targeting either spheres or vesicles as the final copolymer morphology. This powerful characterization technique enables the evolution of particle diameter, mean aggregation number, number of copolymer chains per unit surface area (Sagg) and the distance between adjacent copolymer chains at the core–shell interface (dint) to be monitored as a function of monomer conversion for kinetically-trapped spheres. Moreover, the gradual evolution of copolymer morphology during PISA is confirmed unequivocally, with approximate ‘lifetimes’ assigned to the intermediate pure sphere and worm morphologies when targeting PSMA13–PBzMA150 vesicles. Within vesicle phase space, the membrane thickness (Tm) increases monotonically with PBzMA DP. Furthermore, a combination of dynamic light scattering (DLS), TEM and post mortem SAXS studies indicate that the lumen volume is reduced while the overall vesicle dimensions remain essentially constant. Thus the constrained vesicles grow inwards, as recently reported for an aqueous PISA formulation. This suggests a universal vesicle growth mechanism for all PISA formulations

X-Ray ptychography with a laboratory source

X-ray ptychography has revolutionized nanoscale phase contrast imaging at large-scale synchrotron sources in recent years. We present here the first successful demonstration of the technique in a small-scale laboratory setting. An experiment was conducted with a liquid metal jet x-ray source and a single photon-counting detector with a high spectral resolution. The experiment used a spot size of 5 mu m to produce a ptychographic phase image of a Siemens star test pattern with a submicron spatial resolution. The result and methodology presented show how high-resolution phase contrast imaging can now be performed at small-scale laboratory sources worldwide

Is Carbon Black a Suitable Model Colloidal Substrate for Diesel Soot?

Soot formation in diesel engines is known to cause premature engine wear. Unfortunately, genuine diesel soot is expensive to generate, so carbon blacks are often used as diesel soot mimics. Herein, the suitability of a commercial carbon black (Regal 250R) as a surrogate for diesel soot dispersed in engine base oil is examined in the presence of two commonly used polymeric lubricant additives. The particle size, morphology, and surface composition of both substrates are assessed using BET surface area analysis, TEM, and XPS. The extent of adsorption of a poly(ethylene-co-propylene) (dOCP) statistical copolymer or a polystyrene-block-poly(ethylene-co-propylene) (PS–PEP) diblock copolymer onto carbon black or diesel soot from n-dodecane is compared indirectly using a supernatant depletion assay technique via UV spectroscopy. Thermogravimetric analysis is also used to directly determine the extent of copolymer adsorption. Degrees of dispersion are examined using optical microscopy, TEM, and analytical centrifugation. SAXS studies reveal some structural differences between carbon black and diesel soot particles. The mean radius of gyration determined for the latter is significantly smaller than that calculated for the former, and in the absence of any copolymer, diesel soot suspended in n-dodecane forms relatively loose mass fractals compared to carbon black. SAXS provides evidence for copolymer adsorption and indicates that addition of either copolymer transforms the initially compact agglomerates into relatively loose aggregates. Addition of dOCP or PS–PEP does not significantly affect the structure of the carbon black primary particles, with similar results being observed for diesel soot. In favorable cases, remarkably similar data can be obtained for carbon black and diesel soot when using dOCP and PS–PEP as copolymer dispersants. However, it is not difficult to identify simple copolymer–particle–solvent combinations for which substantial differences can be observed. Such observations are most likely the result of dissimilar surface chemistries, which can profoundly affect the colloidal stability

Polydimethylsiloxane-Based Diblock Copolymer Nano-objects Prepared in Nonpolar Media via RAFT-Mediated Polymerization-Induced Self-Assembly

Monocarbinol-functionalized polydimethylsiloxane (PDMS; mean degree of polymerization = 66) was converted via esterification into a chain transfer agent (CTA) for reversible addition–fragmentation chain transfer (RAFT) polymerization. The degree of esterification was determined to be 94 ± 1% by 1H NMR spectroscopy and 92 ± 1% by UV absorption spectroscopy. This PDMS CTA was then utilized for the dispersion polymerization of benzyl methacrylate (BzMA) in n-heptane at 70 °C. As the PBzMA block grows, it becomes insoluble in the reaction medium, which drives the in situ formation of PDMS–PBzMA diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Depending on the precise reaction conditions, the final diblock copolymer chains can self-assemble to form spheres, worms, or vesicles. Systematic variation of the copolymer concentration and the target degree of polymerization (DP) of the PBzMA block enables construction of a phase diagram that allows the reproducible targeting of pure copolymer morphologies, as judged by transmission electron microscopy and dynamic light scattering studies. 1H NMR spectroscopy studies confirm that relatively high BzMA conversions (>90%) can be achieved within 8 h at 70 °C. Gel permeation chromatography studies (THF eluent) indicate high blocking efficiencies and relatively low final polydispersities (Mw/Mn = 1.14–1.34). Small-angle X-ray scattering (SAXS) has been used to characterize selected examples of the spherical nanoparticles in order to obtain volume-average diameters, which increase monotonically when targeting longer DPs for the core-forming PBzMA block. A relatively high copolymer concentration (>25% w/v) is required to obtain a pure worm phase, which occupies an extremely narrow region within the phase diagram. Selected worm and vesicle dispersions were also analyzed by SAXS, which enables determination of the mean worm cross section, mean worm length and vesicle membrane thickness. In addition, the highly anisotropic worms formed free-standing gels in n-heptane, with rheology measurements indicating viscoelastic behavior and a gel storage modulus of around 104 Pa

Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution

Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering