Harnessing Cytosine for Tunable Nanoparticle Self-Assembly Behavior Using Orthogonal Stimuli.

Nucleobases control the assembly of DNA, RNA, etc. due to hydrogen bond complementarity. By combining these unique molecules with state-of-the-art synthetic polymers, it is possible to form nanoparticles whose self-assembly behavior could be altered under orthogonal stimuli (pH and temperature). Herein, we report the synthesis of cytosine-containing nanoparticles via aqueous reversible addition-fragmentation chain transfer polymerization-induced self-assembly. A poly(N-acryloylmorpholine) macromolecular chain transfer agent (mCTA) was chain-extended with cytosine acrylamide, and a morphological phase diagram was constructed. By exploiting the ability of cytosine to form dimers via hydrogen bonding, the self-assembly behavior of cytosine-containing polymers was altered when performed under acidic conditions. Under these conditions, stable nanoparticles could be formed at longer polymer chain lengths. Furthermore, the resulting nanoparticles displayed different morphologies compared to those at pH 7. Additionally, particle stability post-assembly could be controlled by varying pH and temperature. Finally, small-angle X-ray scattering was performed to probe their dynamic behavior under thermal cycling.

Triggered Polymersome Fusion.

The contents of biological cells are retained within compartments formed of phospholipid membranes. The movement of material within and between cells is often mediated by the fusion of phospholipid membranes, which allows mixing of contents or excretion of material into the surrounding environment. Biological membrane fusion is a highly regulated process that is catalyzed by proteins and often triggered by cellular signaling. In contrast, the controlled fusion of polymer-based membranes is largely unexplored, despite the potential application of this process in nanomedicine, smart materials, and reagent trafficking. Here, we demonstrate triggered polymersome fusion. Out-of-equilibrium polymersomes were formed by ring-opening metathesis polymerization-induced self-assembly and persist until a specific chemical signal (pH change) triggers their fusion. Characterization of polymersomes was performed by a variety of techniques, including dynamic light scattering, dry-state/cryogenic-transmission electron microscopy, and small-angle X-ray scattering (SAXS). The fusion process was followed by time-resolved SAXS analysis. Developing elementary methods of communication between polymersomes, such as fusion, will prove essential for emulating life-like behaviors in synthetic nanotechnology.

Surface-Modified Polypyrrole-Coated PLCL and PLGA Nerve Guide Conduits Fabricated by 3D Printing and Electrospinning.

The efficiency of nerve guide conduits (NGCs) in repairing peripheral nerve injury is not high enough yet to be a substitute for autografts and is still insufficient for clinical use. To improve this efficiency, 3D electrospun scaffolds (3D/E) of poly(l-lactide-co-ε-caprolactone) (PLCL) and poly(l-lactide-co-glycolide) (PLGA) were designed and fabricated by the combination of 3D printing and electrospinning techniques, resulting in an ideal porous architecture for NGCs. Polypyrrole (PPy) was deposited on PLCL and PLGA scaffolds to enhance biocompatibility for nerve recovery. The designed pore architecture of these "PLCL-3D/E" and "PLGA-3D/E" scaffolds exhibited a combination of nano- and microscale structures. The mean pore size of PLCL-3D/E and PLGA-3D/E scaffolds were 289 ± 79 and 287 ± 95 nm, respectively, which meets the required pore size for NGCs. Furthermore, the addition of PPy on the surfaces of both PLCL-3D/E (PLCL-3D/E/PPy) and PLGA-3D/E (PLGA-3D/E/PPy) led to an increase in their hydrophilicity, conductivity, and noncytotoxicity compared to noncoated PPy scaffolds. Both PLCL-3D/E/PPy and PLGA-3D/E/PPy showed conductivity maintained at 12.40 ± 0.12 and 10.50 ± 0.08 Scm-1 for up to 15 and 9 weeks, respectively, which are adequate for the electroconduction of neuron cells. Notably, the PLGA-3D/E/PPy scaffold showed superior cytocompatibility when compared with PLCL-3D/E/PPy, as evident via the viability assay, proliferation, and attachment of L929 and SC cells. Furthermore, analysis of cell health through membrane leakage and apoptotic indices showed that the 3D/E/PPy scaffolds displayed significant decreases in membrane leakage and reductions in necrotic tissue. Our finding suggests that these 3D/E/PPy scaffolds have a favorable design architecture and biocompatibility with potential for use in peripheral nerve regeneration applications.

In Situ Small-Angle X-ray Scattering Studies During Reversible Addition-Fragmentation Chain Transfer Aqueous Emulsion Polymerization.

Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016 , 7 , 5078 - 5090 ). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.

A comprehensive review of electrospinning block copolymers.

Electrospinning provides a versatile and cost-effective route for the generation of continuous nanofibres with high surface area-to-volume ratio from various polymers. In parallel, block copolymers (BCPs) are promising candidates for many diverse applications, where nanoscale operation is exploited, owing to their intrinsic self-assembling behaviour at these length scales. Judicious combination of BCPs (with their ability to make nanosized domains at equilibrium) and electrospinning (with its ability to create nano- and microsized fibres and particles) allows one to create BCPs with high surface area-to-volume ratio to deliver higher efficiency or efficacy in their given application. Here, we give a comprehensive overview of the wide range of reports on BCP electrospinning with focus placed on the use of molecular design alongside control over specific electrospinning type and post-treatment methodologies to control the properties of the resultant fibrous materials. Particular attention is paid to the applications of these materials, most notably, their use as biomaterials, separation membranes, sensors, and electronic materials.

Selective molecular annealing: in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers.

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

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.

Thermally Stabilised Poly(vinyl alcohol) Nanofibrous Materials Produced by Scalable Electrospinning: Applications in Tissue Engineering.

Electrospinning is a widely employed manufacturing platform for tissue engineering applications because it produces structures that closely mimic the extracellular matrix. Herein, we demonstrate the potential of poly(vinyl alcohol) (PVA) electrospun nanofibers as scaffolds for tissue engineering. Nanofibers were created by needleless direct current electrospinning from PVA with two different degrees of hydrolysis (DH), namely 98% and 99% and subsequently heat treated at 180 °C for up to 16 h to render them insoluble in aqueous environments without the use of toxic cross-linking agents. Despite the small differences in the PVA chemical structure, the changes in the material properties were substantial. The higher degree of hydrolysis resulted in non-woven supports with thinner fibres (285 ± 81 nm c.f. 399 ± 153 nm) that were mechanically stronger by 62% (±11%) and almost twice as more crystalline than those from 98% hydrolysed PVA. Although prolonged heat treatment (16 h) did not influence fibre morphology, it reduced the crystallinity and tensile strength for both sets of materials. All samples demonstrated a lack or very low degree of haemolysis (<5%), and there were no notable changes in their anticoagulant activity (≤3%). Thrombus formation, on the other hand, increased by 82% (±18%) for the 98% hydrolysed samples and by 71% (±10%) for the 99% hydrolysed samples, with heat treatment up to 16 h, as a direct consequence of the preservation of the fibrous morphology. 3T3 mouse fibroblasts showed the best proliferation on scaffolds that were thermally stabilised for 4 and 8 h. Overall these scaffolds show potential as 'greener' alternatives to other electrospun tissue engineering materials, especially in cases where they may be used as delivery vectors for heat tolerant additives.

Low cytotoxicity, antibacterial property, and curcumin delivery performance of toughness-enhanced electrospun composite membranes based on poly(lactic acid) and MAX phase (Ti3AlC2).

MXenes, synthesized from their precursor MAX phases, have been extensively researched as additives to enhance the drug delivery performance of polymer matrices, whereas there is a limited number of previous reports on the use of MAX phases themselves for such applications. The use of MAX phases can exclude the complicated synthesis procedure and lessen resultant production and environmental costs required to convert MAX phases to MXenes. Herein, electrospun membranes of poly(lactic acid) (PLA) and a MAX phase (Ti3AlC2) have been fabricated for curcumin delivery. The composite membrane exhibits significantly higher toughness (8.82 MJ m-3) than the plasticized PLA membrane (0.63 MJ m-3) with low cytotoxicity, supporting proliferation of mouse fibroblast L929 cells. The curcumin-loaded composite membrane exhibits high water vapor transmission (∼7350 g m-2 day-1), porosity (∼85 %), water wettability, and antibacterial properties against E. coli and S. aureus. Seven-day curcumin release is enhanced from 45 % (PLA) to 67 % (composite) due to curcumin diffusion from the polymer fibers and MAX phase surface that contributes to overall increased curcumin adsorption and release sites. This work demonstrates the potential of the MAX phase to enhance both properties and curcumin delivery, promising for other eco-friendly systems for sustainable drug delivery applications.

Block copolymer synthesis in ionic liquid via polymerisation-induced self-assembly: a convenient route to gel electrolytes.

We report for the first time a reversible addition-fragmentation chain transfer polymerisation-induced self-assembly (RAFT-PISA) formulation in ionic liquid (IL) that yields worm gels. A series of poly(2-hydroxyethyl methacrylate)-b-poly(benzyl methacrylate) (PHEMA-b-PBzMA) block copolymer nanoparticles were synthesised via RAFT dispersion polymerisation of benzyl methacrylate in the hydrophilic IL 1-ethyl-3-methyl imidazolium dicyanamide, [EMIM][DCA]. This RAFT-PISA formulation can be controlled to afford spherical, worm-like and vesicular nano-objects, with free-standing gels being obtained over a broad range of PBzMA core-forming degrees of polymerisation (DPs). High monomer conversions (≥96%) were obtained within 2 hours for all PISA syntheses as determined by 1H NMR spectroscopy, and good control over molar mass was confirmed by gel permeation chromatography (GPC). Nanoparticle morphologies were identified using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and further detailed characterisation was conducted to monitor rheological, electrochemical and thermal characteristics of the nanoparticle dispersions to assess their potential in future electronic applications. Most importantly, this new PISA formulation in IL facilitates the in situ formation of worm ionogel electrolyte materials at copolymer concentrations >4% w/w via efficient and convenient synthesis routes without the need for organic co-solvents or post-polymerisation processing/purification. Moreover, we demonstrate that the worm ionogels developed in this work exhibit comparable electrochemical properties and thermal stability to that of the IL alone, showcasing their potential as gel electrolytes.

Poly(l-proline)-Stabilized Polypeptide Nanostructures via Ring-Opening Polymerization-Induced Self-Assembly (ROPISA).

Poly(proline) II helical motifs located at the protein-water interface stabilize the three-dimensional structures of natural proteins. Reported here is the first example of synthetic biomimetic poly(proline)-stabilized polypeptide nanostructures obtained by a straightforward ring-opening polymerization-induced self-assembly (ROPISA) process through consecutive N-carboxyanhydride (NCA) polymerization. It was found that the use of multifunctional 8-arm initiators is critical for the formation of nanoparticles. Worm-like micelles as well as spherical morphologies were obtained as confirmed by dynamic light scattering (DLS), transmission electron microscopy (TEM), and small angle X-ray scattering (SAXS). The loading of the nanostructures with dyes is demonstrated. This fast and open-vessel procedure gives access to amino acids-based nanomaterials with potential for applications in nanomedicine.

The relationship between charge density and polyelectrolyte brush profile using simultaneous neutron reflectivity and in situ attenuated total internal reflection FTIR.

We report on a novel experimental study of a pH-responsive polyelectrolyte brush at the silicon/D2O interface. A poly[2-(diethylamino)ethyl methacrylate] brush was grown on a large silicon crystal which acted as both a substrate for a neutron reflectivity solid/liquid experiment but also as an FTIR-ATR spectroscopy crystal. This arrangement has allowed for both neutron reflectivities and FTIR spectroscopic information to be measured in parallel. The chosen polybase brush shows strong IR bands which can be assigned to the N-D(+) stretch, D2O, and a carbonyl group. From such FTIR data, we are able to closely monitor the degree of protonation along the polymer chain as well as revealing information concerning the D2O concentration at the interface. The neutron reflectivity data allows us to determine the physical brush profile normal to the solid/liquid interface along with the corresponding degree of hydration. This combined approach makes it possible to quantify the charge on a polymer brush alongside the morphology adopted by the polymer chains.

Encapsulation of propolis extracts in aqueous formulations by using nanovesicles of lipid and poly(styrene-alt-maleic acid).

Bee propolis has been used in alternative medicine to treat various diseases. Due to its limited water solubility, it is often used in combination with alcohol solvents, causing skin irritation and immune response. To solve this, the new drug delivery system, based on the lipid nanodiscs of 1,2-dimyristoyl-sn-glycero-3-phosphochline (DMPC) and poly(styrene-alt-maleic acid) (PSMA), were created in an aqueous media. At the excess polymer concentrations, the PSMA/DMPC complexation produced the very fine nanoparticles (18 nm). With the increased molar ratio of styrene to maleic acid (St/MA) in the copolymer structure, the lipid nanodisc showed the improved encapsulation efficiency (EE%), comparing to their corresponding aqueous formulations. The maximum value had reached to around 20% when using the 2:1 PSMA precursor. Based on the cytotoxicity test, these nanoparticles were considered to be non-toxic over the low dose administration region (<78 µg/mL). Instead, they possessed the ability to promote the Vero cell growth. The new PSMA/DMPC nanovesicles could thus be used to improve aqueous solubility and therapeutic effects of poorly water-soluble drugs, thus extending their use in modern therapies.

New biomimetic approach for propolis encapsulation was developed with no use of organic solvent.Propolis antioxidants were recovered directly into water-soluble formats.The very fine lipid nanodiscs showed impressive shelf-life stability and tuneable drug-loading capacity.

Assessment of thermally stabilized electrospun poly(vinyl alcohol) materials as cell permeable membranes for a novel blood salvage device.

The use of Intraoperative Cell Salvage (ICS) is currently limited in oncological surgeries, due to safety concerns associated with the ability of existing devices to successfully remove circulating tumour cells. In this work, we present the first stages towards the creation of an alternative platform to current cell savers, based on the extremely selective immunoaffinity membrane chromatography principle. Non-woven membranes were produced via electrospinning using poly(vinyl alcohol) (PVA), and further heat treated at 180 °C to prevent their dissolution in aqueous environments and preserve their fibrous morphology. The effects of the PVA degree of hydrolysis (DH) (98 % vs 99 %), method of electrospinning (needleless DC vs AC), and heat treatment duration (1-8 h) were investigated. All heat treated supports maintained their cytocompatibility, whilst tensile tests indicated that the 99 % hydrolysed DC electrospun mats were stronger compared to their 98 % DH counterparts. Although, and at the described conditions, AC electrospinning produced fibres with more than double the diameter compared to those from DC electrospinning, it was not chosen for subsequent experiments because it is still under development. Evidence of unimpeded passage of SY5Y neuroblastoma cells and undiluted defibrinated sheep's blood in flow-through filtration experiments confirmed the successful creation of 3D networks with minimum resistance to mass transfer and lack of non-specific cell binding to the base material, paving the way for the development of novel, highly selective ICS devices for tumour surgeries.

In Situ Fabrication of Silver Peroxide Hybrid Ultrathin Co-Based Metal-Organic Frameworks for Enhanced Chemodynamic Antibacterial Therapy.

Bacterial-induced infectious diseases have always caused an unavoidable problem and lead to an increasing threat to human health. Hence, there is an urgent need for effective antibacterial strategies to treat infectious diseases. Current methods are often ineffective and require large amounts of hydrogen peroxide (H2O2), with harmful effects on normal healthy tissue. Chemodynamic therapy (CDT) provides an ideal infection microenvironment (IME)-activated paradigm to tackle bacterial-related diseases. To take full advantage of the specificity of IME and enhanced CDT for wounds with bacterial infection, we have designed an intelligent antibacterial system that exploits nanocatalytic ZIF-67@Ag2O2 nanosheets. In this system, silver peroxide nanoparticles (Ag2O2 NPs) were grown on ultrathin zeolitic imidazolate framework-67 (ZIF-67) nanosheets by in situ oxidation, and then, ZIF-67@Ag2O2 nanosheets with the ability to self-generate H2O2 were triggered by the mildly acidic environment of IME. Lamellar ZIF-67 nanosheets were shown to rapidly degrade and release Co2+, allowing the conversion of less reactive H2O2 into the highly toxic reactive oxygen species hydroxyl radicals (•OH) for enhanced CDT antibacterial properties. In vivo results revealed that the ZIF-67@Ag2O2 nanosheet system exhibits excellent antibacterial performance against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria. The proposed hybrid strategy demonstrates a promising therapeutic strategy to enable antibacterial agents with IME-responsive nanocatalytic activity to circumvent antibiotic resistance against bacterial infections.

Evaluation of cell disruption technologies on magnetosome chain length and aggregation behaviour from Magnetospirillum gryphiswaldense MSR-1.

Magnetosomes are biologically-derived magnetic nanoparticles (MNPs) naturally produced by magnetotactic bacteria (MTB). Due to their distinctive characteristics, such as narrow size distribution and high biocompatibility, magnetosomes represent an attractive alternative to existing commercially-available chemically-synthesized MNPs. However, to extract magnetosomes from the bacteria, a cell disruption step is required. In this study, a systematic comparison between three disruption techniques (enzymatic treatment, probe sonication and high-pressure homogenization) was carried out to study their effect on the chain length, integrity and aggregation state of magnetosomes isolated from Magnetospirillum gryphiswaldense MSR-1 cells. Experimental results revealed that all three methodologies show high cell disruption yields (>89%). Transmission electron microscopy (TEM), dynamic light scattering (DLS) and, for the first time, nano-flow cytometry (nFCM) were employed to characterize magnetosome preparations after purification. TEM and DLS showed that high-pressure homogenization resulted in optimal conservation of chain integrity, whereas enzymatic treatment caused higher chain cleavage. The data obtained suggest that nFCM is best suited to characterize single membrane-wrapped magnetosomes, which can be particularly useful for applications that require the use of individual magnetosomes. Magnetosomes were also successfully labelled (>90%) with the fluorescent CellMask™ Deep Red membrane stain and analysed by nFCM, demonstrating the promising capacity of this technique as a rapid analytical tool for magnetosome quality assurance. The results of this work contribute to the future development of a robust magnetosome production platform.

Mild-temperature responsive nanocatalyst for controlled drug release and enhanced catalytic therapy.

Owing to the advantages of the in situ production of toxic agents through catalytic reactions, nanocatalytic therapy has arisen as a highly potential strategy for cancer therapeutics in recent years. However, the insufficient amount of endogenous hydrogen peroxide (H2O2) in the tumor microenvironment commonly limits their catalytic efficacy. Here, we employed carbon vesicle nanoparticles (CV NPs) with high near-infrared (NIR, 808 nm) photothermal conversion efficiency as carriers. Ultrafine platinum iron alloy nanoparticles (PtFe NPs) were grown in situ on the CV NPs, where the highly porous nature of the resultant CV@PtFe NPs was employed to encapsulate a drug, ß-lapachone (La), and phase-change material (PCM). As a multifunctional nanocatalyst CV@PtFe/(La-PCM) NPs can exhibit a NIR-triggered photothermal effect and activate cellular heat shock response, which upregulates the downstream NQO1 via HSP70/NQO1 axis to facilitate bio-reduction of the concurrently melted and released La. Moreover, sufficient oxygen (O2) is supplied by CV@PtFe/(La-PCM) NPs catalyzed at the tumor site to reinforce the La cyclic reaction with abundant H2O2 generation. This promotes the bimetallic PtFe-based nanocatalysis, which breaks H2O2 down into highly toxic hydroxyl radicals (•OH) for catalytic therapy. Our results show that this multifunctional nanocatalyst can be used as a versatile synergistic therapeutic agent with NIR-enhanced nanocatalytic tumor therapy by tumor-specific H2O2 amplification and mild-temperature photothermal therapy, which holds promising potential for targeted cancer treatment. STATEMENT OF SIGNIFICANCE: We present a multifunctional nanoplatform with mild-temperature responsive nanocatalyst for controlled drug release and enhanced catalytic therapy. This work aimed at not only reduce the damage to normal tissues caused by photothermal therapy, but also improves the efficiency of nanocatalytic therapy by stimulating endogenous H2O2 production through photothermal heat. In vitro and in vivo confirmed that CV@PtFe/(La-PCM) NPs exhibited powerful and overall antitumor effects. This formulation may provide an alternative strategy for the development of the mild- photothermal enhanced nanocatalytic therapy effect in solid tumor.

In Situ Compatibilized Blends of PLA/PCL/CAB Melt-Blown Films with High Elongation: Investigation of Miscibility, Morphology, Crystallinity and Modelling.

Ternary-blended, melt-blown films of polylactide (PLA), polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were prepared from preliminary miscibility data using a rapid screening method and optical ternary phase diagram (presented as clear, translucent, and opaque regions) as a guide for the composition selection. The compositions that provided optically clear regions were selected for melt blending. The ternary (PLA/PCL/CAB) blends were first melt-extruded and then melt-blown to form films and characterized for their tensile properties, tensile fractured-surface morphology, miscibility, crystallinity, molecular weight and chemical structure. The results showed that the tensile elongation at the break (%elongation) of the ternary-blended, melt-blown films (85/5/10, 75/10/15, 60/15/25 of PLA/PCL/CAB) was substantially higher (>350%) than pure PLA (ca. 20%). The range of compositions in which a significant increase in %elongation was observed at 55−85% w/w PLA, 5−20% w/w PCL and 10−25% w/w CAB. Films with high %elongation all showed good interfacial interactions between the dispersed phase (PCL and CAB) and matrix (PLA) in FE-SEM and showed improvements in miscibility (higher intermolecular interaction and mixing) and a decrease in the glass transition temperature, when compared to the low %elongation films. The decrease in Mw and Mn and the formation of the new NMR peaks (1H NMR at 3.68−3.73 ppm and 13C NMR at 58.54 ppm) were observed in only the high %elongation films. These are expected to be in situ compatibilizers that are generated during the melt processing, mostly by chain scission. In addition, mathematical modelling was used to study the optimal ratio and cost-effectiveness of blends with optimised mechanical properties. These ternary-blended, melt-blown films have the potential for use in both packaging and medical devices with excellent mechanical performance as well as inherent economic and environmental capabilities.

Synthesis of core-shell polymer particles in supercritical carbon dioxide via iterative monomer addition.

A new, robust methodology for the synthesis of polystyrene-poly(methyl methacrylate) (PS-PMMA) core-shell particles using seeded dispersion polymerisation in supercritical carbon dioxide is reported, where the core-shell ratio can be controlled predictably via manipulation of reagent stoichiometry. The key development is the application of an iterative addition of the MMA shell monomer to the pre-prepared PS core. Analysis of the materials with differing core-shell ratios indicates that all are isolated as single particle populations with distinct and controllable core-shell morphologies.

Transferring Micellar Changes to Bulk Properties via Tunable Self-Assembly and Hierarchical Ordering.

Hierarchical self-assembly is an effective means of preparing useful materials. However, control over assembly across length scales is a difficult challenge, often confounded by the perceived need to redesign the molecular building blocks when new material properties are needed. Here, we show that we can treat a simple dipeptide building block as a polyelectrolyte and use polymer physics approaches to explain the self-assembly over a wide concentration range. This allows us to determine how entangled the system is and therefore how it might be best processed, enabling us to prepare interesting analogues to threads and webs, as well as films that lose order on heating and "noodles" which change dimensions on heating, showing that we can transfer micellar-level changes to bulk properties all from a single building block.