Upcycling of Cereal Byproducts: A Sustainable Opportunity to Valorize Wasted Nutrients and Derive Bioactive Compounds for Humans and Animals Nutrition and Health.

With the global population projected to reach close to 10 billion by 2050, the escalating demand for cereals such as wheat, rice, corn, oat, and barley places significant pressure on production systems. These systems are increasingly vulnerable to the adverse impacts of climate change, threatening global food security. This article emphasizes the critical need to address these challenges and explores strategies for sustainable foodproduction, focusing on the opportunities that the upcycling of cereal byproducts offers for human and animal nutrition and health.

Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures.

Calcium carbonate biomineralization is remarkable for the ability of organisms to produce calcite or aragonite with perfect fidelity, where this is commonly attributed to specific anionic biomacromolecules. However, it is proven difficult to mimic this behavior using synthetic or biogenic anionic organic molecules. Here, it is shown that cationic polyamines ranging from small molecules to large polyelectrolytes can exert exceptional control over calcium carbonate polymorph, promoting aragonite nucleation at extremely low concentrations but suppressing its growth at high concentrations, such that calcite or vaterite form. The aragonite crystals form via particle assembly, giving nanoparticulate structures analogous to biogenic aragonite, and subsequent growth yields stacked aragonite platelets comparable to structures seen in developing nacre. This mechanism of polymorph selectivity is captured in a theoretical model based on these competing nucleation and growth effects and is completely distinct from the activity of magnesium ions, which generate aragonite by inhibiting calcite. Profiting from these contrasting mechanisms, it is then demonstrated that polyamines and magnesium ions can be combined to give unprecedented control over aragonite formation. These results give insight into calcite/aragonite polymorphism and raise the possibility that organisms may exploit both amine-rich organic molecules and magnesium ions in controlling calcium carbonate polymorph.

Positively Charged Additives Facilitate Incorporation in Inorganic Single Crystals.

Incorporation of guest additives within inorganic single crystals offers a unique strategy for creating nanocomposites with tailored properties. While anionic additives have been widely used to control the properties of crystals, their effective incorporation remains a key challenge. Here, we show that cationic additives are an excellent alternative for the synthesis of nanocomposites, where they are shown to deliver exceptional levels of incorporation of up to 70 wt % of positively charged amino acids, polymer particles, gold nanoparticles, and silver nanoclusters within inorganic single crystals. This high additive loading endows the nanocomposites with new functional properties, including plasmon coupling, bright fluorescence, and surface-enhanced Raman scattering (SERS). Cationic additives are also shown to outperform their acidic counterparts, where they are highly active in a wider range of crystal systems, owing to their outstanding colloidal stability in the crystallization media and strong affinity for the crystal surfaces. This work demonstrates that although often overlooked, cationic additives can make valuable crystallization additives to create composite materials with tailored composition-structure-property relationships. This versatile and straightforward approach advances the field of single-crystal composites and provides exciting prospects for the design and fabrication of new hybrid materials with tunable functional properties.

An innovative data processing method for studying nanoparticle formation in droplet microfluidics using X-rays scattering.

X-ray scattering techniques provide a powerful means of characterizing the formation of nanoparticles in solution. Coupling these techniques to segmented-flow microfluidic devices that offer well-defined environments gives access to in situ time-resolved analysis, excellent reproducibility, and eliminates potential radiation damage. However, analysis of the resulting datasets can be extremely time-consuming, where these comprise frames corresponding to the droplets alone, the continuous phase alone, and to both at their interface. We here describe a robust, low-cost, and versatile droplet microfluidics device and use it to study the formation of magnetite nanoparticles with simultaneous synchrotron SAXS and WAXS. Lateral outlet capillaries facilitate the X-ray analysis and reaction times of between a few seconds and minutes can be accommodated. A two-step data processing method is then described that exploits the unique WAXS signatures of the droplets, continuous phase, and interfacial region to identify the frames corresponding to the droplets. These are then sorted, and the background scattering is subtracted using an automated frame-by-frame approach, allowing the signal from the nanoparticles to be isolated from the raw data. Modeling these data gives quantitative information about the evolution of the sizes and structures of the nanoparticles, in agreement with TEM observations. This versatile platform can be readily employed to study a wide range of dynamic processes in heterogeneous systems.

Incorporation of nanogels within calcite single crystals for the storage, protection and controlled release of active compounds.

Nanocarriers have tremendous potential for the encapsulation, storage and delivery of active compounds. However, current formulations often employ open structures that achieve efficient loading of active agents, but that suffer undesired leakage and instability of the payloads over time. Here, a straightforward strategy that overcomes these issues is presented, in which protein nanogels are encapsulated within single crystals of calcite (CaCO3). Demonstrating our approach with bovine serum albumin (BSA) nanogels loaded with (bio)active compounds, including doxorubicin (a chemotherapeutic drug) and lysozyme (an antibacterial enzyme), we show that these nanogels can be occluded within calcite host crystals at levels of up to 45 vol%. Encapsulated within the dense mineral, the active compounds are stable against harsh conditions such as high temperature and pH, and controlled release can be triggered by a simple reduction of the pH. Comparisons with analogous systems - amorphous calcium carbonate, mesoporous vaterite (CaCO3) polycrystals, and calcite crystals containing polymer vesicles - demonstrate the superior encapsulation performance of the nanogel/calcite system. This opens the door to encapsulating a broad range of existing nanocarrier systems within single crystal hosts for the efficient storage, transport and controlled release of various active guest species.

A facile method for generating worm-like micelles with controlled lengths and narrow polydispersity.

This work shows that highly uniform worm micelles formed by polymerisation induced self-assembly can be obtained via simple post-synthesis sonication. Importantly, this straightforward and versatile strategy yields exceptionally monodisperse worms with tunable aspect ratios ranging from 7.2 to 17.6 by simply changing the sonication time.

Hydroxyl-rich macromolecules enable the bio-inspired synthesis of single crystal nanocomposites.

Acidic macromolecules are traditionally considered key to calcium carbonate biomineralisation and have long been first choice in the bio-inspired synthesis of crystalline materials. Here, we challenge this view and demonstrate that low-charge macromolecules can vastly outperform their acidic counterparts in the synthesis of nanocomposites. Using gold nanoparticles functionalised with low charge, hydroxyl-rich proteins and homopolymers as growth additives, we show that extremely high concentrations of nanoparticles can be incorporated within calcite single crystals, while maintaining the continuity of the lattice and the original rhombohedral morphologies of the crystals. The nanoparticles are perfectly dispersed within the host crystal and at high concentrations are so closely apposed that they exhibit plasmon coupling and induce an unexpected contraction of the crystal lattice. The versatility of this strategy is then demonstrated by extension to alternative host crystals. This simple and scalable occlusion approach opens the door to a novel class of single crystal nanocomposites.