Pyrene-functionalized poly(methacrylic acid) acts as an efficient stabilizer for graphene nanoplatelets and facilitates their use in waterborne latex formulations.

HYPOTHESIS: Pyrene derivatives are effective motifs when designing graphene-philic surfactants, enabling the use of hydrophobic graphene-based nanomaterials in waterborne formulations. Hence, novel pyrene end-functionalized polymeric stabilizers show promise for stabilizing aqueous graphene nanomaterial dispersions, and offer benefits over traditional small molecule surfactants. EXPERIMENTS: Pyrene end-functionalized poly(methacrylic acid) (Py-PMAAn, where n = 68 to 128) was synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization of MAA using a pyrene-containing RAFT chain-transfer agent. These polymers were evaluated as aqueous graphene nanoplatelet (GNP) stabilizers. Subsequently, polymer-stabilized GNPs were formulated into film-forming polymer latex dispersions and the properties of the resulting GNP-containing films measured. FINDINGS: Py-PMAAn homopolymers with well-defined molecular weights were prepared via RAFT solution polymerization. They served as efficient stabilizers for aqueous GNP dispersions and performed better than a traditional small molecule surfactant and non-functionalized PMAA, especially at higher pH and with higher molecular weight polymers. The use of Py-PMAAn allowed GNPs to be readily formulated into waterborne latex coatings. When compared to controls, the resulting films were significantly reinforced due to the improved homogeneity of dried nanocomposite films and chain entanglement between the polymer matrix and stabilizers. Thus, the ability to readily incorporate GNPs into aqueous formulations and enhance GNP/polymer matrix interfaces was demonstrated for these novel amphiphilic stabilizers.

Multifunctional Self-Assembled Block Copolymer/Iron Oxide Nanocomposite Hydrogels Formed from Wormlike Micelles.

This article reports the preparation of multifunctional magnetic nanocomposite hydrogels formed from wormlike micelles. Specifically, iron oxide nanoparticles were incorporated into a temperature responsive block copolymer, poly(glycerol monomethacrylate)-b-poly(2-hydroxypropyl methacrylate) (PGMA-b-PHPMA), and graphene oxide (GO) dispersion at a low temperature (∼2 °C) through high-speed mixing and returning the mixture to room temperature, resulting in the formation of nanocomposite gels. The optimal concentrations of iron oxide and GO enhanced the gel strength of the nanocomposite gels, which exhibited a strong magnetic response when a magnetic field was applied. These materials retained the thermoresponsiveness of the PGMA-PHPMA wormlike micelles allowing for a solid-to-liquid transition to occur when the temperature was reduced. The mechanical and rheological properties and performance of the nanocomposite gels were demonstrated to be adjustable, making them suitable for a wide range of potential applications. These nanocomposite worm gels were demonstrated to be relatively adhesive and to act as strain and temperature sensors, with the measured electrical resistance of the nanocomposite gels changing with applied strain and temperature sweeps. The nanocomposite gels were found to recover efficiently after the application of high shear with approximately 100% healing efficiency within seconds. Additionally, these nanocomposite worm gels were injectable, and the addition of GO and iron oxide nanomaterials seemed to have no significant adverse impact on the biocompatibility of the copolymer gels, making them suitable not only for 3D printing in nanocomposite engineering but also for potential utilization in various biomedical applications as an injectable magnetic responsive hydrogel.

pH-Responsive Nanogels Generated by Polymerization-Induced Self-Assembly of a Succinate-Functional Monomer.

Colloidal nanogels formed from a pH-responsive poly(succinate)-functional core and a poly(sulfonate)-functional corona were prepared via a previously unreported reversible addition-fragmentation chain-transfer (RAFT)-mediated aqueous emulsion polymerization-induced self-assembly (PISA) route. Specifically, a poly(potassium 3-sulfopropyl methacrylate) (PKSPMA50) macromolecular chain-transfer agent (macro-CTA) was synthesized via RAFT solution polymerization followed by chain-extension with a hydrophobic, carboxylic acid-functional, 2-(methacryloyloxy) ethyl succinate (MES) monomer at pH 2. Colloidal nanoparticles with tunable diameters between 66 to 150 nm, depending on the core composition, and narrow particle size distributions were obtained at 20% w/w solids. Well-defined pH-responsive nanogels that swell on increasing the pH could be prepared even without the addition of a cross-linking comonomer, and introducing an additional cross-linker to the core led to smaller nanogels with lower swelling ratios. These nanogels could reversibly change in size on cycling the pH between acidic and basic conditions and remain colloidally stable over a wide pH range and at 70 °C.

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization.

Reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to prepare well-defined ABCB tetrablock copolymer nanoparticles via sequential monomer addition at 30 °C. The A block comprises water-soluble poly(2-(N-acryloyloxy)ethyl pyrrolidone) (PNAEP), while the B and C blocks comprise poly(t-butyl acrylate) (PtBA) and poly(n-butyl acrylate) (PnBA), respectively. High conversions are achieved at each stage, and the final sterically stabilized spherical nanoparticles can be obtained at 20% w/w solids at pH 3 and at up to 40% w/w solids at pH 7. A relatively long PnBA block is targeted to ensure that the final tetrablock copolymer nanoparticles form highly transparent films on drying such aqueous dispersions at ambient temperature. The kinetics of polymerization and particle growth are studied using 1H nuclear magnetic resonance spectroscopy, dynamic light scattering, and transmission electron microscopy, while gel permeation chromatography analysis confirmed a high blocking efficiency for each stage of the polymerization. Differential scanning calorimetry and small-angle X-ray scattering studies confirm microphase separation between the hard PtBA and soft PnBA blocks, and preliminary mechanical property measurements indicate that such tetrablock copolymer films exhibit promising thermoplastic elastomeric behavior. Finally, it is emphasized that targeting an overall degree of polymerization of more than 1000 for such tetrablock copolymers mitigates the cost, color, and malodor conferred by the RAFT agent.

Polymer-Assisted 3D Printing of Inductor Cores.

Poly(glycerol monomethacrylate) (PGMA) prepared by reversible addition-fragmentation chain transfer polymerization was investigated as an additive for high-loading iron oxide nanoparticle (IOP) 3D printable inks. The effect of adjusting the molar mass and loading of PGMA on the rheology of IOP suspensions was investigated, and an optimized ink formulation containing 70% w/w IOPs and 0.25% w/w PGMA98 at pH 10 was developed. This ink was successfully 3D printed onto various substrates and into several structures, including rectangles, high aspect ratio cylinders, letters, spiral- and comb-shaped structures, and thin- and thick-walled toroids. The effect of sintering on the mechanical properties of printed artifacts was investigated via four-point flexural and compressive testing, with higher sintering temperatures resulting in improved mechanical properties due to changes in the particle size and microstructure. The printed toroids were fabricated into inductors, and their electrical performance was assessed via impedance spectroscopy at a working frequency range of 0.001-13 MHz. There was a clear trade-off between electrical properties and sintering temperature due to a phase change between γ-Fe2O3 and α-Fe2O3 upon heating. Nevertheless, the optimized devices had a Q factor of ∼40 at 10 MHz, representing a superior performance compared to that of other inductors with iron oxide cores previously reported. Thus, this report represents a significant step toward the development of low-cost, fully aqueous, high loading, and 3D printable ceramic inks for high-performance inductors and functional devices.

Bridging Flocculation of a Sterically Stabilized Cationic Latex as a Biosensor for the Detection of Microbial DNA after Amplification via PCR.

There is a high demand for rapid, sensitive, and accurate detection methods for pathogens. This paper demonstrates a method of detecting the presence of amplified DNA from a range of pathogens associated with serious infections including Gram-negative bacteria, Gram-positive bacteria, and viruses. DNA is amplified using a polymerase chain reaction (PCR) and consequently detected using a sterically stabilized, cationic polymer latex. The DNA induces flocculation of this cationic latex, which consequently leads to rapid sedimentation and a visible change from a milky-white dispersion to one with a transparent supernatant, presenting a clear visible change, indicating the presence of amplified DNA. Specifically, a number of different pathogens were amplified using conventional or qPCR, including Staphylococcus aureus, Escherichia coli, and Herpes Simplex Virus (HSV-2). This method was demonstrated to detect the presence of bacteria in suspension concentrations greater than 380 CFU mL-1 and diagnose the presence of specific genomes through primer selection, as exemplified using methicillin resistant and methicillin susceptible Staphylococcus aureus. The versatility of this methodology was further demonstrated by showing that false positive results do not occur when a PCR of fungal DNA from C. albicans is conducted using bacterial universal primers.

3D printable, thermo-responsive, self-healing, graphene oxide containing self-assembled hydrogels formed from block copolymer wormlike micelles.

Graphene oxide (GO) containing block copolymer nanocomposite hydrogels formed from poly(glycerol monomethacrylate-block-hydroxypropyl methacrylate) (PGMA-PHPMA) wormlike micelles were prepared by either mixing GO and copolymer at low temperature or via in situ reversible addition-fragmentation chain-transfer (RAFT) polymerisation-induced self-assembly (PISA) of HPMA in the presence of a PGMA macromolecular chain-transfer agent and GO flakes. Hydrogels containing 15-25% w/w copolymer and 0 and 8% w/w GO, based on copolymer, were investigated and the maximum gel strength measured was ∼33 kPa for a 25% w/w copolymer gel prepared by in situ polymerisation and containing 2% w/w GO based on copolymer. This gel strength represents a fifteen-fold increase over the same copolymer gel without the addition of GO. The nanocomposite gels were found to recover efficiently after the application of high shear, with up to 98% healing efficiency within seconds. These gels are also 3D printable, self-healing, adhesive and temperature responsive on cooling and re-heating. The observed properties were both GO and copolymer concentration dependent, and tensile testing demonstrated that the nanocomposite gels had higher moduli, elongation at break and toughness than gels prepared without GO.

Preparation of polymer nanoparticle-based complex coacervate hydrogels using polymerisation-induced self-assembly derived nanogels.

This paper reports a generic method to prepare polymer nanoparticle-based complex coacervate (PNCC) hydrogels by employing rationally designed nanogels synthesised by reversible addition-fragmentation chain-transfer (RAFT)-mediated polymerisation-induced self-assembly (PISA). Specifically, a poly(potassium 3-sulfopropyl methacrylate) (PKSPMA) macromolecular chain-transfer agent (macro-CTA) was synthesised via RAFT solution polymerisation followed by chain-extension with a statistical copolymer of benzyl methacrylate (BzMA) and methacrylic acid (MAA) at pH 2. Thus, pH-responsive nanoparticles (NPs) comprising a hydrophobic polyacid core-forming block and a sulfonate-functional stabiliser block were formed. With the introduction of methacrylic acid into the core of the NPs, they become swollen with increasing pH, as judged by dynamic light scattering (DLS), indicating nanogel-type behaviour. PNCC hydrogels were prepared by simply mixing the PISA-derived nanogels and cationic branched polyethyleneimine (bPEI) at 20% w/w. In the absence of MAA in the core of the NPs, gel formation was not observed. The mass ratio between the nanogels and bPEI affected resulting hydrogel strength and a mixture of bPEI and PKSPMA68-P(BzMA0.6-stat-MAA0.4)300 NPs with a mass ratio of 0.14 at pH ∼7 resulted in a hydrogel with a storage modulus of approximately 2000 Pa, as determined by oscillatory rheology. This PNCC hydrogel was shear-thinning and injectable, with recovery of gel strength occurring rapidly after the removal of shear.

Visible label-free detection of bacterial DNA using flocculation of sterically stabilised cationic latexes.

The current gold standard diagnostic for bacterial infections is the use of culture, which can be time consuming and can take up to five days for results to be reported. There is therefore an unmet clinical need for a rapid and label free alternative. This paper demonstrates a method of detecting the presence of amplified DNA from bacterial samples using a sterically-stabilised, cationic polymer latex and widely available equipment, providing an accessible alternative DNA detection technique. If DNA is present in a sample, successful amplification by polymerase chain-reaction (PCR) results in the amplified DNA inducing flocculation of the polymer latex followed by rapid sedimentation. This results in a visible and obvious change from a milky-white dispersion to a precipitated latex with a colourless and transparent supernatant, thus giving a clear visual indication of the presence or absence of amplified DNA. Specifically, the response of four polymer latexes with different morphologies to the addition of amplified bacterial DNA was investigated. Cationic latexes flocculated rapidly whereas non-ionic and anionic latexes did not, as judged by eye, disc centrifuge photosedimentometry (DCP), and UV-visible spectrophotometry. The stability of several cationic latexes with different morphologies in typical PCR reagents was investigated. It was found that unwanted flocculation occurred for a latex with a non-ionic core and a cationic corona (poly[2-vinyl pyridine-b-benzyl methacrylate], prepared by polymerisation-induced self-assembly) whereas a ∼700 nm PEGMA-stabilised P2VP latex (non-ionic stabiliser, cationic core), prepared by emulsion polymerisation remained stable. The sensitivity and rate of sedimentation of the PEGMA-stabilised P2VP latex was demonstrated by varying the sequence length and concentration of amplified DNA from Pseudomonas aeruginosa using universal bacterial primers. DNA concentrations as low as 0.78 ng µl-1 could readily be detected within 30 minutes from the addition of amplified DNA to the latex. Furthermore, the specificity of this method was demonstrated by showing a negative result occurs (no flocculation of the latex) when PCR product from a fungal (Candida albicans) sample using bacterial primers was added to the latex.

Physical Adsorption of Graphene Oxide onto Polymer Latexes and Characterization of the Resulting Nanocomposite Particles.

Polymer/graphene oxide (GO) nanocomposite particles were prepared via heteroflocculation between 140-220 nm cationic latex nanoparticles and anionic GO nanosheets in either acidic or basic conditions. It is demonstrated that nanocomposite particles can be formed using either poly(2-vinylpyridine)-b-poly(benzyl methacrylate) (P2VP-PBzMA) block copolymer nanoparticles prepared by reversible-addition chain-transfer (RAFT)-mediated polymerization-induced self-assembly (PISA), or poly(ethylene glycol)methacrylate (PEGMA)-stabilized P2VP latexes prepared by traditional emulsion polymerization. These two latexes are different morphologically as the P2VP-PBzMA block copolymer latexes have P2VP steric stabilizer chains in their corona, whereas the PEGMA-stabilized P2VP particles have a P2VP core and a nonionic steric stabilizer. Nevertheless, both the P2VP-PBzMA and PEGMA-stabilized P2VP latexes are cationic at low pH. Thus, the addition of GO to these latexes causes flocculation to occur immediately due to the opposite charges between the anionic GO nanosheets and cationic latexes. Control heteroflocculation experiments were conducted using anionic sterically stabilized poly(potassium 3-sulfopropyl methacrylate)-b-poly(benzyl methacrylate) (PKSPMA-PBzMA) and nonionic poly(benzyl methacrylate) (PBzMA) nanoparticles to demonstrate that polymer/GO nanocomposite particles were not formed. The degree of flocculation and the strength of electrostatic interaction between the cationic polymer latexes and GO were assessed using disc centrifuge photosedimentometry (DCP), transmission electron microscopy (TEM), and UV-visible spectrophotometry. These studies suggest that the optimal conditions for the formation of polymer/GO nanocomposite particles were GO contents between 10% and 20% w/w relative to latex, with the latexes containing P2VP in their corona having a stronger electrostatic attraction to the GO sheets.

Preparation and characterisation of graphene oxide containing block copolymer worm gels.

This paper reports a generic method for preparing reinforced nanocomposite worm-gels. Aqueous poly(glycerol monomethacrylate)-b-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) and methanolic poly(glycerol monomethacrylate)-b-poly(benzyl methacrylate) (PGMA-PBzMA) worm gels were prepared by RAFT-mediated polymerisation-induced self-assembly (PISA). The former system undergoes a reversible worm-to-sphere degelation transition upon cooling to 5 °C whilst the latter system undergoes the same transition on heating to 56 °C. This transition allows these copolymer dispersions to be readily mixed with graphene oxide (GO) whilst in a low viscosity state and form nanocomposite gels on returning to room temperature via a sphere-to-worm transition. Various quantities of GO were added to the studied copolymer dispersions at a fixed copolymer content of 15% w/w. A general trend was observed whereby relatively small quantities of GO caused the gel strength of the nanocomposite gel to be higher than that of the pristine worm-gel, as determined by oscillatory rheology. Additional quantities of GO resulted in gel weakening or prevented gel-reformation altogether. For instance, 15% w/w PGMA52-PHPMA130 worm gels had a storage modulus (G') of approximately 1.5 kPa. The addition of 1.5% w/w GO based on the copolymer caused G' to increase to approximately 4.0 kPa but >1.5% w/w GO resulted in gel strengths <1.0 kPa. A combination of aqueous electrophoresis and transmission electron microscopy measurements were used to investigate the mechanism of nanocomposite gel formation. It was observed that the PGMA-based copolymers readily absorb onto the surface of GO. Thus, the role of GO is both to strengthen the worm-gels when an optimal concentration of GO is used, but also prevent worm-reformation if too much copolymer becomes absorbed on the surface of the sheets.

Pyridine-functional diblock copolymer nanoparticles synthesized via RAFT-mediated polymerization-induced self-assembly: effect of solution pH.

Polymerization-induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) polymerization has become widely recognized as a versatile and efficient strategy to prepare complex block copolymer nanoparticles with controlled morphology, size, and surface functionality. In this article, we report the preparation of cationic sterically-stabilized poly(2-vinylpyridine)-poly(benzyl methacrylate) (P2VP-PBzMA) diblock copolymer nanoparticles via RAFT-mediated PISA under aqueous emulsion polymerization conditions. It is demonstrated that the solution pH during PISA has a dramatic effect on the resulting P2VP-PBzMA nanoparticles, as judged by dynamic light scattering (DLS), disc centrifuge photosedimentometry (DCP) and transmission electron microscopy (TEM). Varying the solution pH results in the P2VP stabilizer having different solubilities due to protonation/deprotonation of the pyridine groups. This allows P2VP-PBzMA nanoparticles with tunable diameters to be prepared by altering the DP of the stabilizer (P2VP) and/or core-forming block (PBzMA), or simply by changing the solution pH for a fixed copolymer composition. For example, P2VP-PBzMA nanoparticles with larger diameters can be obtained at higher solution pH as the protonation degree of the P2VP stabilizer has a large effect on both the aggregation of polymer chains during the PISA process, and the resulting behavior of the diblock copolymer nanoparticles. Changing the dispersion pH post-polymerization has a relatively limited effect on particle diameter. Furthermore, aqueous electrophoresis studies indicate that these P2VP-PBzMA nanoparticles had good colloidal stability and high cationic charge (>30 mV) below pH 5 and can be dispersed readily over a wide pH range.

Self-curing super-stretchable polymer/microgel complex coacervate gels without covalent bond formation.

Elastic physical gels are highly desirable because they can be conveniently prepared and readily shaped. Unfortunately, many elastic physical gels prepared in water require in situ free-radical polymerization during the gel formation stage. In contrast, complex coacervate gels are physical gels that can be prepared by simply mixing two pre-formed oppositely-charged polyelectrolytes. However, as far as we are aware, highly elastic complex coacervate gels have not yet been reported. Herein, we combine polyanionic microgel particles with a well-known commercially-available cationic polyelectrolyte to prepare polymer/microgel complex coacervate (PMCC) physical gels. This new family of gels requires annealing at only 37 °C and behaves like a covalent gel but does not form covalent bonds. Thermal reconfiguration of the dynamic ionic bonds transforms the shapeable pre-gel into a highly elastic gel that is super-stretchable, adhesive, self-healing, highly swellable and can be further toughened using Ca2+ as an ionic crosslinker. Our PMCC gels have excellent potential for applications as engineering gels and structural biomaterials, as well as for wound healing and water purification.

Spatially Controlled Occlusion of Polymer-Stabilized Gold Nanoparticles within ZnO.

In principle, incorporating nanoparticles into growing crystals offers an attractive and highly convenient route for the production of a wide range of novel nanocomposites. Herein we describe an efficient aqueous route that enables the spatially controlled occlusion of gold nanoparticles (AuNPs) within ZnO crystals at up to 20 % by mass. Depending on the precise synthesis protocol, these AuNPs can be (i) solely located within a central region, (ii) uniformly distributed throughout the ZnO host crystal or (iii) confined to a surface layer. Remarkably, such efficient occlusion is mediated by a non-ionic water-soluble polymer, poly(glycerol monomethacrylate)70 (G70 ), which is chemically grafted to the AuNPs; pendent cis-diol side groups on this steric stabilizer bind Zn2+ cations, which promotes nanoparticle interaction with the growing ZnO crystals. Finally, uniform occlusion of G70 -AuNPs within this inorganic host leads to faster UV-induced photodegradation of a model dye.

Critical Dependence of Molecular Weight on Thermoresponsive Behavior of Diblock Copolymer Worm Gels in Aqueous Solution.

Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate was used to prepare three poly(glycerol monomethacrylate) x -poly(2-hydroxypropyl methacrylate) y (denoted G x -H y  or PGMA-PHPMA) diblock copolymers, namely G37-H80, G54-H140, and G71-H200. A master phase diagram was used to select each copolymer composition to ensure that a pure worm phase was obtained in each case, as confirmed by transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS) studies. The latter technique indicated a mean worm cross-sectional diameter (or worm width) ranging from 11 to 20 nm as the mean degree of polymerization (DP) of the hydrophobic PHPMA block was increased from 80 to 200. These copolymer worms form soft hydrogels at 20 °C that undergo degelation on cooling. This thermoresponsive behavior was examined using variable temperature DLS, oscillatory rheology, and SAXS. A 10% w/w G37-H80 worm dispersion dissociated to afford an aqueous solution of molecularly dissolved copolymer chains at 2 °C; on returning to ambient temperature, these chains aggregated to form first spheres and then worms, with the original gel strength being recovered. In contrast, the G54-H140 and G71-H200 worms each only formed spheres on cooling to 2 °C, with thermoreversible (de)gelation being observed in the former case. The sphere-to-worm transition for G54-H140 was monitored by variable temperature SAXS: these experiments indicated the gradual formation of longer worms at higher temperature, with a concomitant reduction in the number of spheres, suggesting worm growth via multiple 1D sphere-sphere fusion events. DLS studies indicated that a 0.1% w/w aqueous dispersion of G71-H200 worms underwent an irreversible worm-to-sphere transition on cooling to 2 °C. Furthermore, irreversible degelation over the time scale of the experiment was also observed during rheological studies of a 10% w/w G71-H200 worm dispersion. Shear-induced polarized light imaging (SIPLI) studies revealed qualitatively different thermoreversible behavior for these three copolymer worm dispersions, although worm alignment was observed at a shear rate of 10 s-1 in each case. Subsequently conducting this technique at a lower shear rate of 1 s-1 combined with ultra small-angle x-ray scattering (USAXS) also indicated that worm branching occurred at a certain critical temperature since an upturn in viscosity, distortion in the birefringence, and a characteristic feature in the USAXS pattern were observed. Finally, SIPLI studies indicated that the characteristic relaxation times required for loss of worm alignment after cessation of shear depended markedly on the copolymer molecular weight.

Mechanistic Insights into Diblock Copolymer Nanoparticle-Crystal Interactions Revealed via in Situ Atomic Force Microscopy.

Recently, it has become clear that a range of nanoparticles can be occluded within single crystals to form nanocomposites. Calcite is a much-studied model, but even in this case we have yet to fully understand the details of the nanoscale interactions at the organic-inorganic interface that lead to occlusion. Here, a series of diblock copolymer nanoparticles with well-defined surface chemistries were visualized interacting with a growing calcite surface using in situ atomic force microscopy. These nanoparticles comprise a poly(benzyl methacrylate) (PBzMA) core-forming block and a non-ionic poly(glycerol monomethacrylate) (Ph-PGMA), a carboxylic acid-tipped poly(glycerol monomethacrylate) (HOOC-PGMA), or an anionic poly(methacrylic acid) (PMAA) stabilizer block. Our results reveal three modes of interaction between the nanoparticles and the calcite surface: (i) attachment followed by detachment, (ii) sticking to and "hovering" over the surface, allowing steps to pass beneath the immobilized nanoparticle, and (iii) incorporation of the nanoparticle by the growing crystals. By analyzing the relative contributions of these three types of interactions as a function of nanoparticle surface chemistry, we show that ∼85% of PMAA85-PBzMA100 nanoparticles either "hover" or become incorporated, compared to ∼50% of the HOOC-PGMA71-PBzMA100 nanoparticles. To explain this difference, we propose a two-state binding mechanism for the anionic PMAA85-PBzMA100 nanoparticles. The "hovering" nanoparticles possess highly extended polyelectrolytic stabilizer chains and such chains must adopt a more "collapsed" conformation prior to successful nanoparticle occlusion. This study provides a conceptual framework for understanding how sterically stabilized nanoparticles interact with growing crystals, and suggests design principles for improving occlusion efficiencies.

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.

Self-assembly of poly(lauryl methacrylate)-b-poly(benzyl methacrylate) nano-objects synthesised by ATRP and their temperature-responsive dispersion properties.

Self-assembling poly(lauryl methacrylate)-b-poly(benzyl methacrylate) (PLMAx-PBzMAy) diblock copolymers were synthesised for the first time using solution atom transfer radical polymerisation (ATRP). The PLMA degree of polymerisation (x) was fixed at 14 and the PBzMA degree of polymerisation (y) was varied from 34 to 74. Post-polymerisation transfer of this new series of diblock copolymers from chloroform into n-dodecane (a poor solvent for PBzMA) resulted in self-assembly of polymeric nano-objects. The morphologies for the latter (spheres, worms and vesicles) were controlled by y. The observed morphologies generally agreed with those reported for related PLMAx-PBzMAy diblock copolymers (x ≥ 16) prepared by polymerisation induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) polymerisation (Fielding et al., J. Am. Chem. Soc., 2014, 136, 5790). However, a number of differences were observed such as de-gelation behaviour and the phase boundary positions compared to those expected from Fielding et al. Variable-temperature dynamic light scattering studies for the PLMA14-PBzMA34 spheres revealed that the aggregation number was unaffected by a temperature increase over the range of 20-90 °C, which differed markedly from the behaviour observed for PLMA14-PBzMA64 worms. This difference is a new observation with mechanistic importance for the worm-to-sphere breakdown mechanism. We show that concentrated PLMA14-PBzMAy dispersions (20% w/w) in n-dodecane can be prepared using post-polymerisation transfer. The dispersion with a mixed spherical and worm-like copolymer phase exhibited reversible de-gelation when heated. Surprisingly, the dispersions containing only the worm phase remained as gels (which were white) at temperatures up to 90 °C. Our new ATRP approach for preparing temperature-responsive non-aqueous nano-object dispersions presented here decoupled chain growth and self-assembly and will apply to other copolymer dispersions.

Occlusion of Sulfate-Based Diblock Copolymer Nanoparticles within Calcite: Effect of Varying the Surface Density of Anionic Stabilizer Chains.

Polymerization-induced self-assembly (PISA) offers a highly versatile and efficient route to a wide range of organic nanoparticles. In this article, we demonstrate for the first time that poly(ammonium 2-sulfatoethyl methacrylate)-poly(benzyl methacrylate) [PSEM-PBzMA] diblock copolymer nanoparticles can be prepared with either a high or low PSEM stabilizer surface density using either RAFT dispersion polymerization in a 2:1 v/v ethanol/water mixture or RAFT aqueous emulsion polymerization, respectively. We then use these model nanoparticles to gain new insight into a key topic in materials chemistry: the occlusion of organic additives into inorganic crystals. Substantial differences are observed for the extent of occlusion of these two types of anionic nanoparticles into calcite (CaCO3), which serves as a suitable model host crystal. A low PSEM stabilizer surface density leads to uniform nanoparticle occlusion within calcite at up to 7.5% w/w (16% v/v), while minimal occlusion occurs when using nanoparticles with a high PSEM stabilizer surface density. This counter-intuitive observation suggests that an optimum anionic surface density is required for efficient occlusion, which provides a hitherto unexpected design rule for the incorporation of nanoparticles within crystals.

Determining the Effective Density and Stabilizer Layer Thickness of Sterically Stabilized Nanoparticles.

A series of model sterically stabilized diblock copolymer nanoparticles has been designed to aid the development of analytical protocols in order to determine two key parameters: the effective particle density and the steric stabilizer layer thickness. The former parameter is essential for high resolution particle size analysis based on analytical (ultra)centrifugation techniques (e.g., disk centrifuge photosedimentometry, DCP), whereas the latter parameter is of fundamental importance in determining the effectiveness of steric stabilization as a colloid stability mechanism. The diblock copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using RAFT aqueous emulsion polymerization: this approach affords relatively narrow particle size distributions and enables the mean particle diameter and the stabilizer layer thickness to be adjusted independently via systematic variation of the mean degree of polymerization of the hydrophobic and hydrophilic blocks, respectively. The hydrophobic core-forming block was poly(2,2,2-trifluoroethyl methacrylate) [PTFEMA], which was selected for its relatively high density. The hydrophilic stabilizer block was poly(glycerol monomethacrylate) [PGMA], which is a well-known non-ionic polymer that remains water-soluble over a wide range of temperatures. Four series of PGMA x -PTFEMA y nanoparticles were prepared (x = 28, 43, 63, and 98, y = 100-1400) and characterized via transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS). It was found that the degree of polymerization of both the PGMA stabilizer and core-forming PTFEMA had a strong influence on the mean particle diameter, which ranged from 20 to 250 nm. Furthermore, SAXS was used to determine radii of gyration of 1.46 to 2.69 nm for the solvated PGMA stabilizer blocks. Thus, the mean effective density of these sterically stabilized particles was calculated and determined to lie between 1.19 g cm-3 for the smaller particles and 1.41 g cm-3 for the larger particles; these values are significantly lower than the solid-state density of PTFEMA (1.47 g cm-3). Since analytical centrifugation requires the density difference between the particles and the aqueous phase, determining the effective particle density is clearly vital for obtaining reliable particle size distributions. Furthermore, selected DCP data were recalculated by taking into account the inherent density distribution superimposed on the particle size distribution. Consequently, the true particle size distributions were found to be somewhat narrower than those calculated using an erroneous single density value, with smaller particles being particularly sensitive to this artifact.