Macadamia husks are an underutilized by-product of nut processing and a rich source of phenolic compounds with strong antioxidant activity. However, their instability during processing, storage, and gastrointestinal digestion limits their application in food systems. This study aimed to encapsulate macadamia husk phenolic-rich extract (MHPE) in liposomes to improve stability, enable controlled release, and assess cytotoxicity for functional food applications. MHPE was encapsulated in soy lecithin liposomes using high-shear mixing followed by high-pressure homogenisation. Liposomes were characterized by particle size, polydispersity index (PDI), ζ-potential, encapsulation efficiency, and morphology. Cytotoxicity was evaluated using Caco-2 cells, and phenolic release was assessed under simulated gastrointestinal conditions. MHPE-loaded liposomes exhibited nano-sized particles (77–78 nm), low PDI (0.21), and high negative ζ-potential (−43.11 to −47.01 mV) during two months of storage at 4 °C. Transmission electron microscopy confirmed predominantly spherical vesicles with sizes consistent with dynamic light scattering measurements. Encapsulation efficiency remained high (81.50% initially; 73.60% after 28 days). Both free and extract-loaded liposomes were non-cytotoxic to Caco-2 cells. Encapsulated MHPE showed slower phenolic release compared with the free extract. Overall, liposomal encapsulation effectively enhanced the stability and controlled release of macadamia husk phenolics, supporting their potential use as functional food and nutraceutical ingredients.

Optical force-induced assembly is a promising yet scarcely explored approach for developing functional tools and objects at the microscale, with a wide range of potential applications. Our previous work was the first to investigate the manipulation of these assemblies in the XY plane. Here, we expand on these techniques by systematically exploring optical trap manipulation with the addition of Z-axis control. Manipulation of the Z-axis is referred to as axial displacement and is a viable approach for actively manipulating the assembly morphology. Experiments are conducted for the first time to explore and detail the response of the assembly during active 3D trap manipulation, informing the development of an autonomous control algorithm over the 2D area of the assembly during motion. This control presents techniques to increase assembly stability or alter the area of the assembly for tasks such as passing through constrictions. This work aims to develop the control techniques required to create a unique micromanufacturing approach inspired by the Kilobot thousand-robot swarm.

We have developed innovative core-shell hydrogel capsules with a dual-network shell structure designed for precise control of molecular transport in response to external stimuli such as pH and temperature. The capsules were fabricated using a combination of microfluidic electrospray techniques and water-in-water (w/w) core-shell droplets templating. The primary network of the shell, calcium alginate (Ca-Alg), with a pKa around 3.4, exhibits sensitivity to pH. The secondary network of the shell, poly(ethylene glycol) methyl ether methacrylate (PEGMA), undergoes a volume phase transition near 60 degrees C. These properties enable precise molecular transport control in/out of the capsules by modulating the surface charges through varying pH and modifying pore size through temperature changes. Moreover, the dual-network shell structure not only significantly enhances the mechanical strength of the capsules but also improves their stability under external stimulus, ensuring structural integrity during the transport of molecules. This research lays the groundwork for further investigations into the multimodal stimuli-responsive hydrogel systems to control molecular transport, important in applications such as sensors and reactors for chemical cascade reactions.

In recent years, there has been growing interest in replacing petroleum-based water-in-oil (W/O) emulsifiers with sustainable and less toxic natural materials. Pickering emulsifiers are considered well-suited candidates due to their high interfacial activity and the ability to form emulsions with long-term stability. However, only sporadic examples of natural materials have been considered as inverse Pickering emulsifiers. This study describes the synthesis of a series of hydrophobic cellulose nanospheres by bulk modification with acyl groups of different chain lengths followed by nanoprecipitation, and their application as inverse emulsifiers. Modification with acyl groups of longer chain length (C16, C18) afforded lower degrees of substitution, but resulted in greater thermal stability than groups with shorter acyl chains (C12, C14). Formation of nanospheres with low aspect ratios and narrow size distributions required low initial cellulose concentrations (< 1% w/v), high volumetric ratios of antisolvent to solvent (> 10:1), and slow addition rates (< 20 mL/h). The modified cellulose nanospheres were able to reduce the interfacial tension between water and hexane from 45.8 mN/m to 31.1 mN/m, with an effect that increased with the number of carbons in the added acyl chains. The stearate-modified nanospheres exhibited superhydrophobic behavior, showing a contact angle of 156° ± 4° with water, and demonstrated emulsification performance comparable to the commonly used molecular surfactant sorbitan stearate. Our findings suggest that hydrophobically modified cellulose nanospheres have the potential to be a bio-derived alternative to traditional molecular W/O emulsifiers. Graphical Abstract

This review explores the potential of agri-food waste materials, with a particular focus on macadamia nut by-products. Industrial processing of macadamia nuts yields a significant volume of by-products, including green husk and woody shell. Recent research has highlighted these by-products as readily available, cost-effective rich sources of phenolic compounds, renowned for their potent antioxidant and antibacterial properties. This paper emphasizes the importance of selecting an optimal extraction method to fully harness the bioactive potential of these phenolic compounds. In this work, we provide a comprehensive overview of conventional and advanced extraction techniques that are used to extract phenolic compounds from macadamia by-products, with a particular focus on the methods applied to macadamia green husk. Among the various techniques, it appears that ultrasound-assisted extraction, especially when combined with aqueous organic solvents, is more efficient than other methods for this purpose. This review also addresses the challenges in phenolic compound recovery, primarily due to the lack of a standardized extraction process. This often results in the extensive use of extraction solvents to achieve an extract that is rich in phenolic compounds. Overall, this research offers a valuable understanding of the most effective methods for the extraction and recovery of phenolic compounds from macadamia by-products and discusses the potential for scaling up these extraction processes. Hence, it can serve as a useful resource for researchers and industry professionals interested in sustainable and efficient utilization of by-products of the nut industry.

In recent years, there has been growing interest in replacing petroleum-based water-in-oil emulsifiers with sustainable and less toxic natural materials. Pickering emulsifiers are considered well-suited candidates due to their high interfacial activity and the ability to form emulsions with long-term stability. However, only sporadic examples of natural materials have been considered as inverse Pickering emulsifiers. This study describes the synthesis of a series of esterified cellulose nanospheres and their application as water-in-oil emulsifiers, driven by the vast availability of this biopolymer and its versatility in terms of chemical modification. Hydrophobic nanospheres with low aspect ratios and narrow size distributions were formed by finetuning the conditions for nanoprecipitation, which required low initial cellulose concentrations, high volumetric ratios of antisolvent to solvent, and slow addition rates. The modified cellulose nanospheres were able to reduce the interfacial tension between water and hexane from 45.8 mN/m to 31.1 mN/m, with an effect that increased with the number of carbons in the added acyl chains. The stearate-modified nanospheres exhibited superhydrophobic behavior and demonstrated emulsification performance comparable to the commonly used molecular surfactant sorbitan stearate. Our findings suggest that hydrophobically modified cellulose nanospheres have the potential to be a bio-derived alternative to traditional molecular W/O emulsifiers.

With nearly five decades of per- and polyfluoroalkyl substances (PFASs) being associated with firefighting and industrial activities, these compounds inevitably accumulate in both ground and surface water. PFAS contamination in water has emerged as a significant environmental and public health concern, particularly perfluorooctanesulfonic acid (PFOS), which is often found in higher concentrations compared to other PFAS and has more pronounced adverse health effects. Addressing PFAS contamination requires treating large volumes of water, making technologies that rapidly separate and concentrate PFASs highly favoured. The strong surface activity of PFAS, such as PFOS, enables them to generate colloidal gas aphrons (CGAs) during high shear mixing of their aqueous solutions, where PFASs can be separated and collected as foam. This study aims to evaluate the effectiveness of high shear mixing in separating PFOS from solution, leveraging its accumulation at air-water interfaces. High shear-assisted PFOS separation was tested by varying parameters like rotational speed (4000 to 10,000 rpm), mixing time (30 s to 30 min), and the effect of electrolytes. Results showed greater PFOS separation in the presence of electrolytes, particularly monovalent cations like Na+, compared to divalent cations such as Ca2+, due to the creation of more stable CGAs with smaller sizes. At a mixing rate of 6000 rpm, 85 % of PFOS was removed in 30 s from a highly contaminated PFOS solution (10 mg/L), with over 95 % separation after 5 mixing cycles. While high-shear mixing was efficient in PFOS separation from highly contaminated solutions it was less efficient for low-level contaminated solutions (less than 1 mg/L). These results suggest that hydrodynamic cavitation induced by high-shear mixing seems promising for enhancing the separation of PFOS from heavily contaminated solutions. This technique could serve as a standalone method or be integrated with other PFAS removal technologies to enhance the overall efficiency of PFAS removal from polluted water sources.

Colloidal particles trapped by a focused laser at the air-liquid interface provide an interesting assembly dynamic. In this study, we demonstrated manipulating optical force-induced swarms via dynamic locomotion of assemblies built with holographic optical tweezers. This manipulation approach builds the foundation for autonomous control of building assemblies at the air-liquid interface, which is the first time optical micro-robots have performed this feat. Our proposed semi-autonomous control allows users to produce small dynamic secondary assemblies at the interface, which are transported to and merged with a main static assembly. This static-dynamic approach grows assemblies up to ~2.1 times larger than conventional methods. Manipulation and control of large-scale optical force-induced assemblies in real-time to create re-configurable swarms has the potential to lead the development of new technology and approaches for complex tasks, such as the development of new material, transportation of biological matter, studying biofilm formation created by bacteria colonies at the air-liquid interface, and more.

Levels of native beta-lactoglobulin (β-lg) in heat-treated milk are often used as a measure of quality deterioration. Most kinetic studies to date on β-lg denaturation have been simplified to a single step model, which limits its application in various processing conditions. Furthermore, this denaturation of β-lg is only an initial stage in a series of interactions to take place. In this work, a multistep model for the denaturation of β-lg and its subsequent reaction with κ-casein was developed. This model was used to rationalize the concentrations of native β-lg and κ-casein determined from HPLC. Notably, this model provides a clear account of the influence of β-lg on the loss of micelle-bound κ-casein. The various reaction rates reveal reactions are limited by the rate at which sulfhydryl-disulfide reactions connect proteins while the effect of intermolecular forces is minimal.

Hypothesis: The size, shape and dynamics of assemblies of colloidal particles optically-trapped at an air- water interface can be tuned by controlling the optical potential, particle concentration, surface charge density and wettability of the particles and the surface tension of the solution. Experiments: The assembly dynamics of different colloidal particle types (silica, polystyrene and carboxyl coated polystyrene particles) at an air-water interface in an optical potential were systematically explored allowing the effect of surface charge on assembly dynamics to be investigated. Additionally, the pH of the solutions were varied in order to modulate surface charge in a controllable fashion. The effect of surface tension on these assemblies was also explored by reducing the surface tension of the supporting solution by mixing ethanol with water. Findings: Silica, polystyrene and carboxyl coated polystyrene particles showed distinct assembly beha-viours at the air-water interface that could be rationalised taking into account changes in surface charge (which in addition to being different between the particles could be modified systematically by changing the solution pH). Additionally, this is the first report showing that wettability of the colloidal particles and the surface tension of the solution are critical in determining the resulting assembly at the solution surface. (c) 2022 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

The development of effective strategies to maintain/increase soil C is hindered by the poor process-level understanding of the impact of management practices on C preservation, particularly at different soil depths. Based on the distinct biogeochemistry existing across a soil profile, a depth-dependent response of organic matter (OM) to soil amendments was hypothesized. To test this, we investigated the effect on OM preservation of lime addition to the topsoil and the subsoil of a volcanic soil classified as Andosol - the mineral soil with the largest organic C content worldwide. We incubated samples from each soil layer with (or without) lime addition, in the presence or absence of 13C- and 15N-labeled plant residue (simulating plant C inputs to the soil). The fate of OM in bulk soil and OM-mineral associations of microaggregates was measured using conventional chemical analyses and nano-scale secondary ion mass spectrometry, respectively. The results revealed contrasting geochemical properties existing within the soil profile, i.e. pH and amount of allophane increasing with soil depth. Functional complexity of OM also increased with depth, as revealed by an increase in spatial and molecular heterogeneity of OM, i.e. a larger proportion of microbial-derived OM with high spatial separation found in the subsoil. Lime addition caused OM destabilization as denoted by the increase in the amount of water-extractable C in both the topsoil and the subsoil (P < 0.05). In the topsoil, OM coverage of mineral surfaces decreased with liming from 49% to 30% whereas the opposite was observed in the subsoil, where it increased from 23% to 29%. Thus, liming caused the disruption of OM-mineral associations within microaggregates in the topsoil, but not in the subsoil. We infer that, at depth, the OM destabilization involved the mobilization of OM previously protected within macroaggregates. This pulse of labile C generated an advantageous environment for microbial OM mineralization in the subsoil, but this effect was diluted in the topsoil, richer in OM and where OM functional complexity is smaller. Depth-dependent soil geochemical properties and functional complexity determine differences in the effect of liming on the fate of soil OM in top vs. subsoils.

Emulsions yield and flow (or lose their shape) when sufficient stress is applied to force the drops to move past each other. The drops in emulsions stabilised by nanoparticles do not move all at once, unlike in emulsions stabilised by surfactants. This is because particles that are not attached to the oil-water interface can aggregate into networks in the continuous phase. The networks around the drops must be disrupted before the drops can move. We used a combination of steady and oscillatory shear, and creep measurements to probe Pickering emulsion yielding behaviour at different drop volume fractions. We characterised the heterogeneous structure of the emulsions on the micro- and nano-scale using confocal fluorescence and electron microscopy techniques. A key finding is that two processes occur during the transition from solid to fluid flow in Pickering emulsions. This is best revealed by oscillatory measurements. We also found evidence of structure recovery in emulsions while they were being sheared. These results have implications for designing Pickering emulsions which retain their shape, rather than slumping.

Knowledge of the key factors regulating soil organic carbon (OC) mineralization in response to fertilizers and lime application is essential to understanding the effects of agricultural land management on soil OC preservation. Microbial community composition and OC availability to microorganisms have been proposed as the two most imperative factors controlling soil OC mineralization, although their relative importance is still under debate. Here we performed a laboratory incubation in combination with high-throughput sequencing and structural equation modeling to examine the mechanisms underlying the responses of OC mineralization in the topsoil and the subsoil of a volcanic soil (an Andosol) to the additions of lime and/or phosphate. Results showed that lime and/or phosphate additions induced distinct shifts in the microbial community composition and functional profiles in the topsoil and the subsoil. We found that OC mineralization relied on microbial community composition and functionality in the topsoil but was strongly related to the quality and quantity of the water-extractable OC (indicative of the OC availability) in the subsoil. These data suggest that the key regulator controlling the response of OC mineralization to lime and/or P additions shifts from microbial community composition to OC availability as soil depth increases in the Andosol. Our findings highlight the central role of mechanisms controlling soil OC mineralization in regulating the responses of mineralization to intensive agricultural management practices.

Structural manipulation of β-lactoglobulin through processes such as heat treatment and complexation with other molecules has proven fruitful in industrial formulations. To fully appreciate the ramifications of such methods on protein interfacial adsorption we have investigated assemblies of β-lactoglobulin at oil/water interfaces predominantly at pH 3 and at different conditions of ionic strength, salt type and temperature. These parameters were tuned to vary the relative amounts of two native species, namely, monomer and its smallest aggregate, the dimer, while the interface was monitored using rheology and tensiometry. Unfolding of β-lactoglobulin at the interface triggers the formation of disulfide linkages between the free thiol groups of two monomers which are located at cys121. In this way, monomers pair up to form discrete assemblies of two β-lactoglobulin molecules (non-native dimers) that are not interconnected further and this is reflected in the absence of a viscoelastic layer in solutions with high monomer concentrations. Native dimers however form primary particles capable of forming two thiol bonds allowing the formation of extended networks. A higher concentration of dimers increases the final interfacial elastic strength of the network. This fundamental relation between the quaternary structure of β-lg and its subsequent interfacial network suggests a possible interfacial role in its biological function.

Electrostatic complexation of negatively charged polysaccharides with β-lactoglobulin (β-lg) has been shown to bolster the protein films at oil/water interfaces thereby improving emulsion stability. However, recent sub-phase exchange experiments demonstrated that highly charged polysaccharides such as low methyl-esterified pectin are complementary only if sequentially introduced to a pre-formed interfacial β-lg film. In this study, results of transient interfacial shear rheology show that, by using high-methylesterified pectins instead, complexes can be formed in pre-mixed solutions with β-lg at pH 4 that can lead to reinforced protein films at dodecane/water interfaces. Using this one-shot adsorption of such complexes, pectins as well as short chain polysaccharides like homogalacturonan nearly doubled the steady state shear elastic moduli as compared to that of a pure β-lg film. The lag times of film formation were established to be primarily decided by the charge density and pattern on the polysaccharide. Based on the results from mixed solutions of β-lg monomers, it is proposed that the polysaccharide at pH 4 strengthens the resulting interfacial layer by concatenating adsorbed β-lg molecules thereby establishing cross-links in the aqueous phase.

Within the nucleus of the eukaryotic cell, DNA is partitioned into domains of highly condensed, transcriptionally silent heterochromatin and less condensed, transcriptionally active euchromatin. Heterochromatin protein 1α (HP1α) is an architectural protein that establishes and maintains heterochromatin, ensuring genome fidelity and nuclear integrity. Although the mechanical effects of changes in the relative amount of euchromatin and heterochromatin brought about by inhibiting chromatin-modifying enzymes have been studied previously, here we measure how the material properties of the nuclei are modified after the knockdown of HP1α. These studies were inspired by the observation that poorly invasive MCF7 breast cancer cells become more invasive after knockdown of HP1α expression and that, indeed, in many solid tumors the loss of HP1α correlates with the onset of tumor cell invasion. Atomic force microscopy (AFM), optical tweezers (OT), and techniques based on micropipette aspiration (MA) were each used to characterize the mechanical properties of nuclei extracted from HP1α knockdown or matched control MCF7 cells. Using AFM or OT to locally indent nuclei, those extracted from MCF7 HP1α knockdown cells were found to have apparent Young’s moduli that were significantly lower than nuclei from MCF7 control cells, consistent with previous studies that assert heterochromatin plays a major role in governing the mechanical response in such experiments. In contrast, results from pipette-based techniques in the spirit of MA, in which the whole nuclei were deformed and aspirated into a conical pipette, showed considerably less variation between HP1α knockdown and control, consistent with previous studies reporting that it is predominantly the lamins in the nuclear envelope that determine the mechanical response to large whole-cell deformations. The differences in chromatin organization observed by various microscopy techniques between the MCF7 control and HP1α knockdown nuclei correlate well with the results of our measured mechanical responses and our hypotheses regarding their origin.

The mechanisms by which lime and/or phosphate addition impacts the preservation of soil organic matter (OM) are poorly understood. We explored the changes in quantity and chemistry of water-extractable organic matter (WEOM) in the bulk soil and its heavy density fraction (>1.6 g/cm3) of an unmanaged C-rich volcanic soil caused by lime and/or phosphate application. The addition of lime or phosphate caused (i) a significant increase in the WEOM, along with a decrease in its C/N ratio and an increase in its aromaticity, and (ii) changes in the WEOM chemical composition, measured with pyrolysis-gas chromatography/mass spectrometry, this being most impacted by lime application. The combined effect of lime and phosphate addition on the quantity and chemistry of WEOM was larger than the effects of separate lime and phosphate additions. By comparing the response of the bulk soil and the heavy fraction, we infer that phosphate has a greater contribution to the destabilization of vulnerable particulate OM, while lime causes a comparable disruption in the particulate OM and that in the heavy fraction. These findings provide a mechanistic insight into the decreased OM stability after liming and/or P fertilizing Andosols. They have implications for designing climate-smart management practices for these soils.

Organogels are often made from solutions of proteins, polymers or fatty acids in oil. The macromolecular species crystallize, or assemble, into mesh structures that inhibit oil flow. This review focuses on using fumed silica nanoparticles as an alternative structuring agent. Fumed silica particles have a unique, branched morphology that means the particles aggregate into three-dimensional, interconnected networks. Two key aspects for formulating edible oleogels are addressed. Advances in our understanding of fumed silica particle aggregation in oil that point toward strategies for tuning the rheological properties of oleogels are examined. Secondly, the factors likely to affect the lipolysis of oils structured used fumed silica particles, and hence the bioavailability of ingredients loaded into the gels, are discussed. The next challenge for these promising materials is to target suitable applications for their use as fat replacement in foods.

Depositing drops of a nanoparticle suspension onto a substrate is a simple way to model the processes that occur during printing of macroscopic structures from nanoparticles. We investigated the effect of adding short chain length amines on the deposit patterns formed by fused silica nanoparticles. Adding amphiphiles which adsorb at the particle surfaces is expected to modify their wettability and stability. Hence it should be possible to tune the particle interactions and control the patterns formed by the deposited particles. We probed the effects of amine adsorption on the silica particles by measuring the changes to the electrokinetic properties and wettability of the particles. Adding short chain amines to concentrated dispersions of silica nanoparticles induces a transition from a ring-shaped morphology to a more uniform, dot-shaped deposit during evaporative drying. We characterised the size and shape of deposits formed as a function of amphiphile chain length and concentration, and the particle concentration. The variation in the deposition pattern with the alkyl chain length can be accounted for by considering the effect of amine adsorption on the interactions between the particles and the interactions between the particles and the substrate. This is the first report showing how short chain alkylamines can be used to tune the deposition of silica nanoparticles.

This chapter describes the development of novel biomaterials based on nanoparticles for encapsulating and controlling the release of drug compounds and other bioactive ingredients. The materials discussed are fabricated by assembling nanoparticles together at the fluid interfaces in emulsion templates. They are divided into five categories; nanoparticle-stabilised emulsions, colloidal capsules, macroporous scaffolds, lipid-nanoparticle hybrids and polymer films. The focus of the chapter is on analysing how key surface properties of the nanoparticle layers affect the processes by which the emulsion templates are transformed into biomaterials for oral and dermal delivery of drugs. Finally, the progress made towards in vivo and in vitro testing of the new materials being developed is assessed.