HYPOTHESIS: Previous use of linear elastic fracture mechanics to estimate toughness of wet particulate materials underestimates the toughness because it does not account for plastic deformation as a dissipation mechanism. Plastic deformation is responsible for the majority of energy dissipated during the fracture of wet colloidal particulate materials. Plastic deformation around the crack tip increases with saturation of the particulate body. The toughness of the body increases with increasing saturation. EXPERIMENTS: Elastic plastic fracture mechanics using the J-integral approach was used for the first time to measure the fracture toughness (JIC) of wet micron sized alumina powder bodies as a function of saturation. The samples were prepared by slip casting. The saturation was controlled by treatment in a humidity chamber. The elastic modulus (E) and the energy dissipated by plastic flow (Apl) were measured in uniaxial compression. The critical stress intensity factor (KIC) was measured using a diametral compression sample with a flaw of known size. The fracture toughness (JIC) was calculated from these measured quantities and the geometry of the specimen. FINDINGS: Elastic plastic fracture mechanics was used for the first time to quantitively account for plastic deformation of wet particulate materials. The linear elastic fracture mechanics approach previously used accounted for less than 1% of the total energy dissipated in fracture. Toughness (JIC) was found to increase with increasing saturation due to plastic deformation that increased with saturation level. The improved understanding of toughness as a function of saturation will aid in providing quantitative analysis of cracking in drying colloidal films and bodies.

There is a need for effective vaccine delivery systems and vaccine adjuvants without extraneous excipients that can compromise or minimize their efficacy. Vaccine adjuvants cytosine-phosphate-guanosine oligodeoxynucleotides (CpG ODNs) can effectively activate immune responses to secrete cytokines. However, CpG ODNs are not stable in serum due to enzymatic cleavage and are difficult to transport through cell membranes. Herein, DNA microcapsules made of CpG ODNs arranged into 3D nanostructures are developed to improve the serum stability and immunostimulatory effect of CpG. The DNA microcapsules allow encapsulation and co-delivery of cargoes, including glycogen. The DNA capsules, with >4 million copies of CpG motifs per capsule, are internalized in cells and accumulate in endosomes, where the Toll-like receptor 9 is engaged by CpG. The capsules induce up to 10-fold and 20-fold increases in tumor necrosis factor (TNF)-α and interleukin (IL)-6 secretion, respectively, in RAW264.7 cells compared with CpG ODNs. Furthermore, the microcapsules stimulate TNF-α and IL-6 secretion in a concentration- and time-dependent manner. The immunostimulatory activity of the capsules correlates to their intracellular trafficking, endosomal confinement, and degradation, assessed by confocal and super-resolution microscopy. These DNA capsules can serve as both adjuvants to stimulate an immune reaction and vehicles to encapsulate vaccine peptides/genes to achieve synergistic immune effects.

Developing materials with programmable permeability for cargo encapsulation and release is challenging but important in a number of fields including drug delivery and sensing. Metal–phenolic networks (MPNs) are an emerging class of hybrid coordination materials with pH-responsiveness and modularity that can be engineered into functional thin films for diverse applications. Herein, we engineer MPN-based microcapsules with a dynamic gating mechanism by adjusting the intermolecular interactions in the capsules. Altering the choice of building blocks and precursor ratio provides an intrinsic and modular means of tailoring capsule size and permeability. Alternatively, regulating the pH of the environment, and thereby the protonation states of MPNs, extrinsically enables capsules to switch between highly permeable (>90% of capsules permeable at pH 9) and near-impermeable (<20% at pH 3) states. These findings provide insights into the dynamic nature of MPNs and offer a route to engineer smart delivery systems and selective gating materials.

Biosourced nanoparticles have a range of desirable properties for therapeutic applications, including biodegradability and low immunogenicity. Glycogen, a natural polysaccharide nanoparticle, has garnered much interest as a component of advanced therapeutic materials. However, functionalizing glycogen for use as a therapeutic material typically involves synthetic approaches that can negatively affect the intrinsic physiological properties of glycogen. Herein, the protein component of glycogen is examined as an anchor point for the photopolymerization of functional poly(N-isopropylacrylamide) (PNIPAM) polymers. Oyster glycogen (OG) nanoparticles partially degrade to smaller spherical particles in the presence of protease enzymes, reflecting a population of surface-bound proteins on the polysaccharide. The grafting of PNIPAM to the native protein component of OG produces OG-PNIPAM nanoparticles of ∼45 nm in diameter and 6.2 MDa in molecular weight. PNIPAM endows the nanoparticles with temperature-responsive aggregation properties that are controllable and reversible and that can be removed by the biodegradation of the protein. The OG-PNIPAM nanoparticles retain the native biodegradability of glycogen. Whole blood incubation assays revealed that the OG-PNIPAM nanoparticles have a low cell association and inflammatory response similar to that of OG. The reported strategy provides functionalized glycogen nanomaterials that retain their inherent biodegradability and low immune cell association.

Recovering valuable materials from food waste by applying the concept of a bio-refinery is attracting considerable interest. To this effect, we investigated the possibility of enhancing the enzymatic hydrolysis of food waste using ultrasonic technology. The effect of pre-treating blended food waste with high-intensity ultrasound (20 kHz) on subsequent hydrolysis by glucoamylase was investigated as a function of sonication time and temperature. Particle sizing by laser diffraction, and imaging via scanning electronic microscopy showed that ultrasonic pre-treatment could reduce the particle size of the blended food waste significantly, resulting in a better interaction with the enzyme. As a consequence, the glucose yield of enzymatic hydrolysis was ∼10% higher for food waste pre-sonicated using the most intensive ultrasonication conditions studied (5 min sonication at a power of 0.8 W/mL at 20 °C) than for the untreated control. In addition, the time required to achieve high yields of glucose could be more than halved using ultrasonic pre-treatment. This could enable the hydrolysis reactor size or the enzyme usage to be reduced by more than 50%. Therefore, an ultrasound-assisted bioconversion process from food waste into a value-added product has been demonstrated.

A systematic investigation of the emulsifying properties of ruptured algae cells was performed for the first time. The slurry of ruptured algae cells was separated into different biomass fractions, namely the cell debris, the delipidated debris, the serum, and the lipid. The interfacial interactions of these biomass fractions with a nonpolar solvent (e.g. hexane or hexadecane) were characterized using pendant drop tensiometry and interfacial shear rheology. The stability of the different emulsions (formed by the different biomass fractions) was tested using analytical centrifugation. The extracted lipid was an excellent surfactant that reduced the interfacial tension, however, it was not effective at stabilizing the emulsions. The protein-rich serum produced a strong interfacial film that stabilized the emulsions against coalescence during centrifugation. The cell debris stabilized the emulsions to a lesser extent by adsorbing to the droplet surface, presumably via interactions with hydrophobic extracellular polymeric substances (EPS). However, neither the serum nor the cell debris were very effective surfactants, and required the presence of the lipid fraction to produce small emulsion droplets. When present together, the components exhibited competitive interfacial adsorption, which influenced emulsion stability. In particular, the interruption of the protein film by the presence of lipid or cell debris reduced the stability of the emulsions. This study provides a new mechanistic understanding of emulsification during wet lipid extraction from microalgae that will be useful for determining strategies to improve solvent recovery. The results also suggest potential for developing effective bioemulsifiers or biosurfactants from fractionated microalgae biomass for commercial application.

With an increasing global energy demand, along with a rising uptake of portable electronic devices, it is of great importance to investigate the viability of alternative energy harvesting technologies. Flexible piezoelectric generators (PEGs) are able to convert mechanical energy to electricity, making them an ideal candidate to decrease reliance on conventional energy sources and to power flexible, portable and implantable electronics. In this study, we show a low-energy production pathway for transparent PEGs based on poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) via shear-induced alignment of its dipoles through extrusion printing, complemented by spatial dipolar templating onto single-walled carbon nanotubes (SWCNTs) at low concentrations (<0.05 wt%). The resulting composite PEGs show up to a 500% enhancement in the piezoelectric charge coefficient d33 relative to extrusion printed pristine PVDF-TrFE, with similar enhancements in energy harvesting, exhibiting a power density of up to 20 μW cm−3 at 0.02 wt% SWCNTs. The extrusion printed composite PEGs show recyclability using only a green solvent (acetone) and are found to exhibit piezoelectric energy harvesting with a power density of up to 71 μW cm−3 upon reprinting, overcoming two of the most significant hurdles towards commercial production of flexible PEGs.

The effect of ultrasonication on the cell rupture of marine microalgae Nannochloropsis sp. was studied as a function of the slurry solids concentration and treatment time. The concentrated viscous wet-biomass (~12 to 25% solids concentration) was subjected to ultrasonication (20 kHz) at 3.8 W/mL for up to 5 min. Compared to extraction without cell rupture, sonication led to a significant increase in lipid yield from ~11% to about 70% within 5 min of sonication. The extraction yield was found to decrease with increased solids concentration, with a large decrease between 20% to 25% solids. This is attributed to the increase in viscosity and decrease in speed of sound with increase in solids. The ultrasound attenuation coefficient increased 320-fold as the solids increased from 20 to 25%. Such a large attenuation of ultrasound places a limit of 20% solids to be used for cell rupture by ultrasound. The specific energy requirements per unit mass of extracted lipid were lowest at 20% solids. At lower concentrations energy was wasted heating water, at higher concentrations the lipid yields were reduced due to ultrasound attenuation.

Ultrasound standing waves can be used to separate emulsions. So far, they have been applied to oil-in-water emulsions with low continuous phase viscosity. This technique has the potential to be used for novel applications such as separating lipids from algal biomass; however, this requires the methodology to be optimized to process viscous emulsions. We have addressed this issue by studying the effects of bulk phase viscosity (1–23 mPa·s), emulsion droplet size (4.5–20 μm), power (10–54 W/L), and frequency (1 and 2 MHz) of ultrasound on the separation efficiency of model mineral oil-in-water–glycerol-mixture emulsions. For the small droplet size (4.5 μm) emulsion in water, the maximum separation achieved increased from 36 to 79% when ultrasound power increased from 10 to 54 W/L. However, for the large droplet size (11 μm) emulsion, the maximum separation was greater than 95% and was independent of ultrasound power. The maximum separation efficiency for small droplet size (4.5–6 μm) emulsions decreased from 80 to 14% when the viscosity increased from 1 to 23 mPa·s. However, for the large droplet size (11–20 μm) emulsion, the maximum separation efficiency decreased from 98 to 62% when the viscosity of the bulk phase was increased from 1 to 23 mPa·s. The experimental results were then interpreted using analytical and numerical simulations by calculating the time required for the emulsion droplets to migrate to the nearest pressure antinodal plane under the influence of ultrasound standing waves. Further experiments showed that increasing the ultrasound frequency from 1 to 2 MHz increased the maximum separation from 36 to 86% for fine emulsions and water as the continuous phase.

Dissipative self-assembly processes were recently exploited to assemble synthetic materials into supramolecular structures. In most cases, chemical fuel or light driven self-assembly of synthetic molecules was reported. Herein, experimental and computational approaches were used to unveil the role of acoustic cavitation in the formation of supramolecular nanoaggregates by dissipative self-assembly. Acoustic cavitation bubbles were employed as an energy source and a transient interface to fuel and refuel the dissipative self-assembly of simple aromatic biomolecules into uniform nanoparticles. Molecular dynamics simulations were applied to predict the formation of metastable aggregates and the dynamic exchange of the interacting molecules in the nanoaggregates. The intracellular trafficking and dissipative dissolution of the nanoparticles were tracked by microscopy imaging.

Neurodegenerative diseases are generally characterized by a progressive loss of neuronal subpopulations, with no available cure to date. One of the main reasons for the limited clinical outcomes of new drug formulations is the lack of appropriate in vitro human cell models for research and validation. Stem cell technologies provide an opportunity to address this challenge by using patient-derived cells as a platform to test various drug formulations, including particle-based drug carriers. The therapeutic efficacy of drug delivery systems relies on efficient cellular uptake of the carrier and can be dependent on its size, shape, and surface chemistry. Although considerable efforts have been made to understand the effects of the physiochemical properties of particles on two-dimensional cell culture models, little is known of their effect in three-dimensional (3D) cell models of neurodegenerative diseases. Herein, we investigated the role of particle size (235-1000 nm), charge (cationic and anionic), and density (1.05 and 1.8 g cm-3) on the interactions of particles with human embryonic stem cell-derived 3D cell cultures of sensory neurons, called sensory neurospheres (sNSP). Templated layer-by-layer particles, with silica or polystyrene cores, and self-assembled glycogen/DNA polyplexes were used. Particles with sizes <280 nm effectively penetrated sNSP. Additionally, effective plasmid DNA delivery was observed up to 6 days post-transfection with glycogen/DNA polyplexes. The findings provide guidance in nanoparticle design for therapies aimed at neurodegenerative diseases, in particular Friedreich's ataxia, whereby sensory neurons are predominantly affected. They also demonstrate the application of 3D models of human sensory neurons in preclinical drug development.

The predicted strong piezoelectricity for monolayers of group IV monochalcogenides, together with their inherent flexibility, makes them likely candidates for developing flexible nanogenerators. Within this group, SnS is a potential choice for such nanogenerators due to its favourable semiconducting properties. To date, access to large-area and highly crystalline monolayer SnS has been challenging due to the presence of strong inter-layer interactions by the lone-pair electrons of S. Here we report single crystal across-the-plane and large-area monolayer SnS synthesis using a liquid metal-based technique. The characterisations confirm the formation of atomically thin SnS with a remarkable carrier mobility of ~35 cm2 V-1 s-1 and piezoelectric coefficient of ~26 pm V-1. Piezoelectric nanogenerators fabricated using the SnS monolayers demonstrate a peak output voltage of ~150 mV at 0.7% strain. The stable and flexible monolayer SnS can be implemented into a variety of systems for efficient energy harvesting.