From fundamental insights to rational (bio)polymer nanocomposite design - Connecting the nanometer to meter scale.

Nanoparticle addition has the potential to make bioplastic use mainstream, as the resultant nanocomposite shows improved mechanical, barrier, and thermal properties. It is well established that the architecture and dynamics of the nanoparticle-polymer interphasial region, ∼ 1.5-9 nm from the nanoparticle surface, are crucial for nanocomposite characteristics. Yet, how these molecular phenomena translate to the bulk is still largely unknown. A multi-disciplinary and multi-scale vision is required to capture the full picture and improve materials far beyond what is currently possible. In this review, a first step in bridging the apparent gap between fundamental insights toward observed material properties is made. At the molecular scale, the polymer chain density and dynamics at the nanoparticle surface are governed by a complex interplay between enthalpy and entropy. The resultant interphasial properties can only be propagated to the macroscopic scale effectively when the nanoparticles are well-distributed. This makes the dispersion state a key parameter for which thermodynamic and kinetic insights can be used to prevent nanoparticle aggregation. These insights are linked to material properties relevant to packaging. The outlook section elaborates on the remaining challenges and the steps required to further understand and better design nanocomposite systems.

Particle dispersion governs nano to bulk dynamics for tailored nanocomposite design.

Nanoparticle addition can expand bioplastic use, as the resultant nanocomposite features e.g., improved mechanical properties. HYPOTHESIS: It is generally hypothesised that the nanoparticle-polymer interaction strength is pivotal to reduce polymer dynamics within the interphasial region and beyond. EXPERIMENTS: Translating nanoscale phenomena to bulk properties is challenging, as traditional techniques that probe interphasial dynamics are limited to well-dispersed systems. Laser speckle imaging (LSI) enabled us to probe interphasial nanoscale dynamics of samples containing aggregated nanoparticles. We relate these LSI-derived relaxation times to bulk rheological properties at a micro scale. FINDINGS: Nanocomposites with well-dispersed PDMS-coated titanium dioxide nanoparticles of ∼100 nm showed higher viscosities than nanocomposites containing aggregated PVP- and PAA-coated nanoparticles of 200-2000 nm. Within the interphasial region, nanoparticle addition increased relaxation times by a factor 101-102, reaching ultraslow relaxations of ∼103 s. While the viscosity increased upon nanoparticle loading, interphasial relaxation times plateaued at 5 wt% for nanocomposites containing well-dispersed nanoparticles and 10 wt% for nanocomposites containing aggregated nanoparticles. Likely, interphasial regions between nanoparticles interact, which is more prominent in systems with well-dispersed nanoparticles and at higher loadings. Our results highlight that, contrary to general belief, nanoparticle dispersion seems of greater importance for mechanical reinforcement than the interaction between polymer and particle.

Novel oral microscope gives mechanistic insights into colloidal drivers of friction in oral biofilms.

Texture and mouthfeel are central to the sensory enjoyment of food and beverages. Yet our incomplete understanding of how food boluses are transformed in the mouth limits our texture prediction ability. As well as thin film tribology, the interaction of food colloids with the oral tissue and salivary biofilms plays a key role in texture perception via mechanoreceptors in the papillae. In this study we describe the development of an oral microscope capable of quantitative characterization of the inactions of food colloids with papillae and their concurrent saliva biofilm. We also highlight how the oral microscope revealed key microstructural drivers of several topical phenomena (oral residue formation, coalescence in-mouth, grittiness of protein aggregates and finally microstructural origin of polyphenol astringency) in the domain of texture creation. The coupling of a fluorescent food grade dye with image analysis enabled specific and quantitative determination of the microstructural changes in mouth. Emulsions either underwent no aggregation, small aggregation, or extensive aggregation depending on whether their surface charge facilitated complexation with the saliva biofilm. Quite surprisingly cationic gelatin emulsions that were already aggregated with saliva in mouth underwent coalescence if subsequently exposed to tea polyphenols (EGCG). Large protein aggregates were found to aggregate with the saliva coated papillae, increasing their size tenfold and possibly explaining why there are perceived as gritty. An exciting observation was the oral microstructural changes that occurred upon exposure to tea polyphenols (EGCG). Filiform papillae shrunk, and the saliva biofilm was seen to precipitate/collapse, exposing a very rough tissue surface. These tentative early steps are the first in vivo microstructural insights into the different food oral transformations that are drivers of key texture sensation.

Comparison of the Degree of Acetylation of Chitin Nanocrystals Measured by Various Analysis Methods.

Chitin and its derivate chitosan have versatile properties and have been used in various applications. One key parameter determining the functionality of chitin-based materials is the degree of acetylation (DA). For DA determination, NMR and FTIR spectroscopy are often considered to be the gold standard, but these techniques may not always be available and are rather time-consuming and costly. The first derivative UV method has been suggested, although accurate measurements can be challenging for materials with high degrees of acetylation, due to hydroxymethylfurfural (HMF) formation and other side reactions occurring. In this paper, we re-evaluated the first derivate UV method for chitin and chitosan powder, chitin nanocrystals, and deacetylated chitin nanocrystals. Our results showed that the first derivative UV method is capable of measuring DA with high accuracy (>0.9), leading to values comparable to those obtained by 1H NMR, 13C NMR, and FTIR. Moreover, by-product formation could either be suppressed by selecting the proper experimental conditions, or be compensated. For chitin nanocrystals, DA calculation deviations up to 20% due to by-product formation can be avoided with the correction that we propose. We conclude that the first derivative UV method is an accessible method for DA quantification, provided that sample solubility is warranted.

Chitin Nanocrystals Provide Antioxidant Activity to Polylactic Acid Films.

About 1/3rd of produced food goes to waste, and amongst others, advanced packaging concepts need to be developed to prevent this from happening. Here, we target the antioxidative functionality of food packaging to thus address food oxidation without the need for the addition of antioxidants to the food product, which is not desirable from a consumer point of view. Chitin nanocrystals (ChNC) have been shown to be promising bio-fillers for improving the mechanical strength of biodegradable plastics, but their potential as active components in plastic films is rather unexplored. In the current study, we investigate the antioxidant activity of chitin nanocrystals as such and as part of polylactic acid (PLA) films. This investigation was conducted using DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging activity. Chitin nanocrystals produced via acid hydrolysis showed five times higher activity compared to crude chitin powder. When using these crystals as part of a polylactic acid film (either inside or on top), in both scenarios, antioxidant activity was found, but the effect was considerably greater when the particles were at the surface of the film. This is an important proof of the principle that it is possible to create biodegradable plastics with additional functionality through the addition of ChNC.

Chitin Nanocrystal Hydrophobicity Adjustment by Fatty Acid Esterification for Improved Polylactic Acid Nanocomposites.

Bioplastics may solve environmental issues related to the current linear plastic economy, but they need improvement to be viable alternatives. To achieve this, we aimed to add chitin nanocrystals (ChNC) to polylactic acid (PLA), which is known to alter material properties while maintaining a fully bio-based character. However, ChNC are not particularly compatible with PLA, and surface modification with fatty acids was used to improve this. We used fatty acids that are different in carbon chain length (C4-C18) and degree of saturation (C18:2). We successfully used Steglich esterification and confirmed covalent attachment of fatty acids to the ChNC with FTIR and solid-state 13C NMR. The morphology of the ChNC remained intact after surface modification, as observed by TEM. ChNC modified with C4 and C8 showed higher degrees of substitution compared to fatty acids with a longer aliphatic tail, while particles modified with the longest fatty acid showed the highest hydrophobicity. The addition of ChNC to the PLA matrix resulted in brown color formation that was reduced when using modified particles, leading to higher transparency, most probably as a result of better dispersibility of modified ChNC, as observed by SEM. In general, addition of ChNC provided high UV-protection to the base polymer material, which is an additional feature that can be created through the addition of ChNC, which is not at the expense of the barrier properties, or the mechanical strength.

Colloidal dynamics of emulsion droplets in mouth.

The interaction of emulsions with the tongue is key to the sensory appeal of food and can potentially be exploited for oral/buccal pharmaceutical delivery. Whilst there is good understanding of the different mucoadhesive forces governing emulsion interaction with the tongue, their relative importance is not well understood. In addition, the physical location of emulsions within the saliva papillae on the tongue is not understood at all. A combination of ex vivo salivary film, and in vivo oral coating experiments were used to determine the importance of different mucoadhesive forces. Mucoadhesion of cationic emulsions was largely driven by electrostatic complexation. SDS-PAGE of the in vivo saliva coating highlighted that mucins were largely responsible for cationic emulsion mucoadhesion. Anionic emulsions were bound via hydrophobic/steric interactions to small salivary proteins typically located away from the mucin anchor points. The physical location and clustering of emulsions relative to the salivary film/papillae was probed via the invention of a fluorescent oral microscope. Cationic emulsions were densely clustered close to the papillae whilst anionic emulsions were suspended in the salivary film above the papillae. Interestingly, non-ionic emulsions were also trapped within the salivary film above the papillae as individual droplets. These findings highlight that whilst electrostatic complexation with saliva is a powerful mucoadhesive force, hydrophobic and steric interactions also act to induce oral retention of emulsions. The differences in physical location and clustering of emulsions within the salivary film hint at the 3D locations of the different salivary proteins driving each mucoadhesive interaction. This novel understanding of emulsion saliva/papillae interactions has potential to aid efficacy of buccal pharmaceutical delivery and the reduction of astringency in plant-based foods.

Quantification of energy input required for chitin nanocrystal aggregate size reduction through ultrasound.

Nanoparticles have been claimed to contribute efficiently to e.g. the mechanical strength of composite materials when present as individual particles. However, these particles tend to aggregate. In this paper we prepare nanocrystals from chitin, a product with high potential added value for application in bio-based materials, and investigate the effect of ultrasound on de-aggregation. Chitin nanocrystals with a length ~ 200 nm and a diameter ~ 15 nm, were obtained via acid hydrolysis of crude chitin powder. Freeze drying resulted in severe aggregation and after redispersion sizes up to ~ 200 µm were found. Ultrasound treatment was applied and break up behaviour was investigated using static light scattering, dynamic light scattering, and laser diffraction. Our results suggest that the cumulative energy input was the dominant factor for chitin nanocrystal aggregate breakup. When a critical energy barrier of ~ 100 kJ/g chitin nanocrystals was exceeded, the chitin nanocrystal aggregates broke down to nanometre range. The break up was mostly a result of fragmentation: the aggregation energy of chitin nanocrystal aggregates was quantified to be ~ 370 kJ/g chitin nanocrystals and we hypothesize that mainly van der Waals interactions and hydrogen bonds are responsible for aggregation.

Thermoplastic bio-nanocomposites: From measurement of fundamental properties to practical application.

Although the discovery of plastic has revolutionized materials used in many industries and by consumers, their non-biodegradable nature has led to one of the greatest problems of our times: plastic waste in the environment. Bioplastics which are biobased and biodegradable, have been suggested as alternatives for their fossil based counterparts, but their properties often do not meet the requirements that standard plastics would, and are in clear need of improvement. One way to do so is by the addition of nanoparticles which, when homogeneously dispersed, have been reported to result in great improvements. However, in practice, homogenous distribution of nanoparticles is not that trivial due to their tendency to aggregate, also after addition to the polymer matrix. Although theoretical frameworks to prevent this process are available, we feel that the options explored in practice are often rather trial and error in nature. For that reason, we review the theories available, aiming to facilitate the design of the nanocomposites for a sustainable future. We first discuss thermodynamic frameworks which revolve around nanoparticle aggregation. To minimize nanoparticle aggregation, the nanoparticle and polymer can be selected in such a way that they have similar polar and dispersive surface energies. The second part is dedicated to nanocomposite processing, where kinetic effects act on the nanocomposite material therewith influencing its final morphology, although it is good to point out that other factors such as reaggregation also affect the final nanocomposite morphology. The third section is dedicated to how nanoparticles affect the polymer matrix to which they are added. We describe how interactions at an atomic scale, result in the formation of an interphasial region which ultimately leads to changed bulk material properties. From these three sections, we conclude that three parameters are often overlooked when designing nanocomposites, namely the surface energies of the nanoparticles and polymers, the aggregation bond energy or strength, and the interphase region. Therefore, in the fourth section we provide an overview of techniques to identify these three parameters. We finish with a summery and outlook for the design of bio nanocomposites, where we bring all insights from the previous four sections together.