Recent Advances in Solid-State Modification for Thermoplastic Polymers: A Comprehensive Review.

This review introduces groundbreaking insights in polymer science, specifically spotlighting a novel review of the solid-state modification (SSM) approach of thermoplastic polymers, a method not extensively explored. Unlike traditional melt polymer modification, SSM stands out by incorporating monomers or oligomers into the amorphous phase of polymers through innovative exchange reactions. The background of the study places thermoplastics within the context of their increased use over the past century, highlighting their versatility in various applications and the associated environmental and health concerns due to certain additives. The results section outlines the unique aspects of SSM and its increasing recognition for its potential to enhance material performance in areas such as catalysts and composites. It also discusses the application of SSM in modifying different thermoplastic polymers, highlighting various studies demonstrating the method's effectiveness in altering polymer properties. Finally, this work emphasizes SSM's importance in environmental sustainability and its potential in the recycling and upcycling of plastic materials. It acknowledges the challenges and future perspectives in the field, particularly regarding the scalability of SSM techniques for industrial applications and their role in advancing a circular economy in the polymer industry.

Covalent Adaptable Networks through Dynamic N,S-Acetal Chemistry: Toward Recyclable CO2-Based Thermosets.

Finding new chemistry platforms for easily recyclable polymers has become a key challenge to face environmental concerns and the growing plastics demand. Here, we report a dynamic chemistry between CO2-sourced alkylidene oxazolidones and thiols, delivering circular non-isocyanate polyurethane networks embedding N,S-acetal bonds. The production of oxazolidone monomers from CO2 is facile and scalable starting from cheap reagents. Their copolymerization with a polythiol occurs under mild conditions in the presence of a catalytic amount of acid to furnish polymer networks. The polymer structure is easily tuned by virtue of monomer design, translating into a wide panel of mechanical properties similar to commodity plastics, ranging from PDMS-like elastomers [with Young's modulus (E) of 2.9 MPa and elongation at break (εbreak) of 159%] to polystyrene-like rigid plastics (with E = 2400 MPa, εbreak = 3%). The highly dissociative nature of the N,S-acetal bonds is demonstrated and exploited to offer three different recycling scenarios to the thermosets: (1) mechanical recycling by compression molding, extrusion, or injection molding─with multiple recycling (at least 10 times) without any material property deterioration, (2) chemical recycling through depolymerization, followed by repolymerization, also applicable to composites, and (3) upcycling of two different oxazolidone-based thermosets into a single one with distinct properties. This work highlights a new facile and scalable chemical platform for designing highly dynamic polymer networks containing elusive oxazolidone motifs. The versatility of this chemistry shows great potential for the preparation of materials (including composites) of tuneable structures and properties, with multiple end-of-life scenarios.

Balancing the Strength-Impact Relationship and Other Key Properties in Polypropylene Copolymer-Natural CaSO4 (Anhydrite)-Filled Composites.

To develop novel mineral-filled composites and assess their enhanced properties (stiffness, a good balance between mechanical strength and impact resistance, greater temperature stability), a high-impact polypropylene copolymer (PPc) matrix containing an elastomeric discrete phase was melt mixed with natural CaSO4 ß-anhydrite II (AII) produced from gypsum rocks. First, in a prior investigation, the PPc composites filled with AII (without any modification) displayed enhanced stiffness, which is correlated with the relative content of the filler. The tensile and impact strengths dramatically decreased, especially at high filling (40 wt.%). Therefore, two key methods were considered to tune up their properties: (a) the ionomeric modification of PPc composites by reactive extrusion (REx) with zinc diacrylate (ZA), and (b) the melt mixing of PPc with AII surface modified with ethylenebis(stearamide) (EBS), which is a multifunctional processing/dispersant additive. The properties of composites produced with twin-screw extruders (TSEs) were deeply assessed in terms of morphology, mechanical, and thermal performance, including characterizations under dynamic mechanical solicitations at low and high temperatures. Two categories of products with distinct properties are obtained. The ionomeric modification by Rex (evaluated by FTIR) led to composites characterized by remarkable thermal stability, a higher temperature of crystallization, stronger interfacial interactions, and therefore noticeable mechanical properties (high tensile strength (i.e., 28 MPa), increased stiffness, moderate (3.3 kJ/m2) to good (5.0 kJ/m2) impact resistance) as well as advanced heat deflection temperature (HDT). On the other hand, the surface modification of AII with EBS facilitated the dispersion and debonding of microparticles, leading to composites revealing improved ductility (strain at break from 50% to 260%) and enhanced impact properties (4.3-5.3 kJ/m2), even at high filling. Characterized by notable mechanical and thermal performances, high whiteness, and a good processing ability, these new PPc-AII composites may be tailored to meet the requirements of end-use applications, ranging from packaging to automotive components.

Adding Value in Production of Multifunctional Polylactide (PLA)-ZnO Nanocomposite Films through Alternative Manufacturing Methods.

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)-ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA-ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1-3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA-ZnO nanocomposites.

Interfacial Compatibilization into PLA/Mg Composites for Improved In Vitro Bioactivity and Stem Cell Adhesion.

The present work highlights the crucial role of the interfacial compatibilization on the design of polylactic acid (PLA)/Magnesium (Mg) composites for bone regeneration applications. In this regard, an amphiphilic poly(ethylene oxide-b-L,L-lactide) diblock copolymer with predefined composition was synthesised and used as a new interface to provide physical interactions between the metallic filler and the biopolymer matrix. This strategy allowed (i) overcoming the PLA/Mg interfacial adhesion weakness and (ii) modulating the composite hydrophilicity, bioactivity and biological behaviour. First, a full study of the influence of the copolymer incorporation on the morphological, wettability, thermal, thermo-mechanical and mechanical properties of PLA/Mg was investigated. Subsequently, the bioactivity was assessed during an in vitro degradation in simulated body fluid (SBF). Finally, biological studies with stem cells were carried out. The results showed an increase of the interfacial adhesion by the formation of a new interphase between the hydrophobic PLA matrix and the hydrophilic Mg filler. This interface stabilization was confirmed by a decrease in the damping factor (tanδ) following the copolymer addition. The latter also proves the beneficial effect of the composite hydrophilicity by selective surface localization of the hydrophilic PEO leading to a significant increase in the protein adsorption. Furthermore, hydroxyapatite was formed in bulk after 8 weeks of immersion in the SBF, suggesting that the bioactivity will be noticeably improved by the addition of the diblock copolymer. This ceramic could react as a natural bonding junction between the designed implant and the fractured bone during osteoregeneration. On the other hand, a slight decrease of the composite mechanical performances was noted.

Interphase Design of Cellulose Nanocrystals/Poly(hydroxybutyrate-ran-valerate) Bionanocomposites for Mechanical and Thermal Properties Tuning.

Poly[(3-hydroxybutyrate)-ran-(3-hydroxyvalerate)] (PHBV) is a bacterial polyester with a strong potential as a substitute for oil-based thermoplastics due to its biodegradability and renewability. However, its inherent slow crystallization rate limits its thermomechanical properties and therefore its applications. In this work, surface-modified cellulose nanocrystals (CNCs) have been investigated as green and biosourced nucleating and reinforcing agent for PHBV matrix. Different ester moieties from the CNCs were thereby produced through a green one-pot hydrolysis/Fisher esterification. Beyond the improved dispersion, the CNCs surface esterification affected the thermal and thermomechanical properties of PHBV. The results demonstrate that butyrate-modified CNCs, mimicking the PHBV chemical structure, brought a considerable improvement toward the CNCs/matrix interface, leading to an enhancement of the PHBV thermomechanical properties via a more efficient stress transfer, especially above its glass transition.

A Review on Liquid Crystal Polymers in Free-Standing Reversible Shape Memory Materials.

Liquid crystal polymers have attracted massive attention as stimuli-responsive shape memory materials due to their unique reversible large-scale and high-speed actuations. These materials can be utilized to fabricate artificial muscles, sensors, and actuators driven by thermal order-disorder phase transition or trans-cis photoisomerization. This review collects most commonly used liquid crystal monomers and techniques to macroscopically order and align liquid crystal materials (monodomain), highlighting the unique materials on the thermal and photo responsive reversible shape memory effects. Challenges and potential future applications are also discussed.

Processing of PVDF-based electroactive/ferroelectric films: importance of PMMA and cooling rate from the melt state on the crystallization of PVDF beta-crystals.

Poly(vinylidene difluoride) (PVDF) displays attractive ferroelectric/piezoelectric properties and its polar ß-crystals are specifically targeted for achieving electroactive applications. However, their direct crystallization from the melt state represents a challenging task that has never been addressed using melt-state processes. The use of poly(methyl methacrylate) (PMMA) is herein investigated to promote the PVDF polar ß-phase using melt-blending and extrusion-calendering technologies. The presence of the ß-phase is here confirmed by ATR-FTIR and WAXS experiments with blends at a PMMA content as low as 5 wt%. The key role of PMMA for the ß-phase crystallization from the melt state was unambiguously highlighted with the help of Flash DSC experiments in non-isothermal cooling mode from the melt state. PMMA is able to efficiently shift the α-to-ß crystal transition to lower cooling rates (>100-200 °C s-1), making the achievement of the PVDF polar ß-phase for these blends compatible with conventional processing tools. A crystal phase diagram is proposed for the PVDF/PMMA blends to highlight the dual effects of both PMMA and cooling rate on the PVDF crystallization during melt-processing. Ferroelectric properties were even observed for the blends containing PMMA up to 10 wt% with the highest remanent polarization obtained at 5 wt% PMMA. After 10 wt% PMMA, a progressive transition from ferroelectric to pseudo-linear dielectric behavior is observed more likely due to the presence of PMMA in the interlamellar amorphous phase of the polar PVDF spherulites as shown by SAXS experiments. In this work, we successfully demonstrated that PMMA plays a key role in the crystallization of PVDF polar crystals from the melt state, enabling large-scale and continuous extrusion processing of PVDF-based materials with attractive dielectric properties for sensing and harvesting applications.

Dynamic Iminoboronate-Based Boroxine Chemistry for the Design of Ambient Humidity-Sensitive Self-Healing Polymers.

Developing intrinsic self-healing polymeric materials is of great interest nowadays to extend material lifetime and/or prevent the replacement of damaged pieces. Spontaneously humidity-sensitive healable polymer network built around dynamic covalent B-O bonds was templated by using iminoboronate-based boroxine derivatives. Taking advantage of the dynamic boroxine/boronic acid equilibrium and iminoboronate chemistry, it is possible to construct polymeric materials able to self-heal without requiring any energy-demanding external activation. Interestingly, this novel family of iminoboronate adduct-based materials can be readily produced by a relatively simple and straightforward synthesis between boronic acid and diamine-based compounds, paving the way to coatings that are self-healable at ambient humidity.

Polylactide/Poly(ω-hydroxytetradecanoic acid) Reactive Blending: A Green Renewable Approach to Improving Polylactide Properties.

A green manufacturing technique, reactive extrusion (REx), was employed to improve the mechanical properties of polylactide (PLA). To achieve this goal, a fully biosourced PLA based polymer blend was conceived by incorporating small quantities of poly(ω-hydroxytetradecanoic acid) (PC14). PLA/PC14 blends were compatibilized by transesterification reactions promoted by 200 ppm titanium tetrabutoxide (Ti(OBu)4) during REx. REx for 15 min at 150 rpm and 200 °C resulted in enhanced blend mechanical properties while minimizing losses in PLA molecular weight. SEM analysis of the resulting compatibilized phase-separated blends showed good adhesion between dispersed PC14 phases within the continuous PLA phase. Direct evidence for in situ synthesis of PLA-b-PC14 copolymers was obtained by HMBC and HSQC NMR experiments. The size of the dispersed phase was tuned by the screw speed to "tailor" the blend morphology. In the presence of 200 ppm Ti(OBu)4, inclusion of only 5% PC14 increased the elongation at break of PLA from 3 to 140% with only a slight decrease in the tensile modulus (3200 to 2900 MPa). Furthermore, PLA's impact strength was increased by 2.4× that of neat PLA for 20% PC14 blends prepared by REx. Blends of PLA and PC14 are expected to expand the potential uses of PLA-based materials.

Differentiation of petro-sourced plastic microfilaments from organic microfilaments by SEM-EDX in environmental samples.

Quantifying microplastics (MPs) in marine environments is challenging due to the complexities of differentiation from other materials. This study aims to distinguish petro-sourced plastic microfilaments from organic ones in environmental samples using scanning electron microscope coupled with energy dispersive X-ray (SEM-EDX) analysis. Therefore, 38 particles resembling MPs (PRMPs) from sediments and organisms in Madagascar were analyzed. MPs identification thresholds were determined from SEM-EDX analysis of macroplastics and seaweed, the primary sources of microfilaments. SEM-EDX results of the 38 PRMPs were compared with identification/misidentification made by five MPs observation experts. Results indicated that a carbon/oxygen (C/O) ratio >1 distinguished macroplastics and MPs from other sources (seaweed and organic microfilaments). SEM-EDX analysis identified 81.58% of PRMPs as MPs. The average error made by one observer was 36.32%. These findings highlight the need for a method to assess identification error in MPs quantification and recommend SEM-EDX analysis of microfilaments to gauge observer error.

Biobased polyesters with composition-dependent thermomechanical properties: synthesis and characterization of poly(butylene succinate-co-butylene azelate).

Environmentally friendly poly(butylenesuccinate-co-butyleneazelate) (P(BS-co-BAz)s) aliphatic copolyesters with composition-dependent thermomechanical properties were synthesized from succinic acid (SuA), 1,4-butanediol (BDO), and dimethylazelate (DMAz) through a two-step polycondensation reaction. The molar SuA/AzA ratio was varied from 4:1 to 1:4, and the chemical structure and molecular characteristics of resulting (co)polyesters were characterized by NMR and SEC, whereas thermal properties and crystallinity were studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analyses (DMTA), and X-ray diffraction (XRD). A good agreement between theoretical and experimental SuA/AzA molar ratios in the copolyesters was achieved, together with the recovery of semicrystalline random copolymers of uniform composition along the chains. NMR, DSC, DMTA, and XRD results show that depending on their composition the P(BS-co-BAz) copolyesters might find applications from elastomers to high-impact thermoplastics.

Long-term immersion of compostable plastics in marine aquarium: Microbial biofilm evolution and polymer degradation.

The best-selling compostable plastics, polylactic acid (PLA) and polybutylene adipate-co-terephthalate (PBAT), can accidentally end up in the marine environment due to plastic waste mismanagement. Their degradation and colonization by microbial communities are poorly documented in marine conditions. To better understand their degradation, as well as the dynamics of bacterial colonization after a long immersion time (99, 160, and 260 days), PBAT, semicrystalline, and amorphous PLA films were immersed in a marine aquarium. Sequencing and chemical analyses were used in parallel to characterize these samples. Despite the variation in the chemical intrinsic parameters of these plastics, their degradation remains very slow. Microbial community structure varied according to the immersion time with a high proportion of Archaea. Moreover, the plastisphere structure of PBAT was specific. A better understanding of compostable plastic degradability is crucial to evaluate their impact on ecosystems and to eco-design new recyclable plastics with optimal degradation properties.

Balancing Acute and Chronic Occupational Risks: The Use of Nitrile Butadiene Rubber Undergloves by Firefighters to Reduce Exposure to Toxic Contaminants.

Firefighters are exposed via multi-route exposure to a multitude of chemicals (PAHs, VOCs, flame retardants, dioxins, etc.) that may cause acute and long-term health effects. The dermal absorption of contaminants is a major contributor to the overall exposure and can be reduced by wearing appropriate personal protective equipment. As leather firefighters' gloves cannot be decontaminated regularly by wet cleaning, many Belgian firefighters wear supplementary undergloves made of nitrile butadiene rubber (NBR) to protect against the accumulation of toxicants. However, the safety of this practice has been questioned. In this commentary, the current practice and risks are outlined for the first time, assessed by an interdisciplinary working group of the Belgian Superior Health Council. As NBR sticks to the skin more at high temperatures, the contact time on removal will be prolonged, posing an additional risk for deeper burns. However, based on the physicochemical properties of NBR and the existing experience of firefighters and burn centers, it is estimated that such incidents occur relatively rarely in practice. On the other hand, the risk of repeated exposure to contaminated gloves if no undergloves are worn is unacceptable. Despite the slightly increased risk for deeper burns, it is concluded that wearing disposable NBR gloves under regular firefighters' gloves is an appropriate and effective preventive measure against toxic contamination. The nitrile butadiene rubber must always be fully covered to avoid any contact with the heat.

Ionically Modified Gelatin Hydrogels Maintain Murine Myogenic Cell Viability and Fusion Capacity.

For tissue engineering of skeletal muscles, there is a need for biomaterials which do not only allow cell attachment, proliferation, and differentiation, but also support the physiological conditions of the tissue. Next to the chemical nature and structure of the biomaterial, its response to the application of biophysical stimuli, such as mechanical deformation or application of electrical pulses, can impact in vitro tissue culture. In this study, gelatin methacryloyl (GelMA) is modified with hydrophilic 2-acryloxyethyltrimethylammonium chloride (AETA) and 3-sulfopropyl acrylate potassium (SPA) ionic comonomers to obtain a piezoionic hydrogel. Rheology, mass swelling, gel fraction, and mechanical characteristics are determined. The piezoionic properties of the SPA and AETA-modified GelMA are confirmed by a significant increase in ionic conductivity and an electrical response as a function of mechanical stress. Murine myoblasts display a viability of >95% after 1 week on the piezoionic hydrogels, confirming their biocompatibility. The GelMA modifications do not influence the fusion capacity of the seeded myoblasts or myotube width after myotube formation. These results describe a novel functionalization providing new possibilities to exploit piezo-effects in the tissue engineering field.

Protecting public health and the environment: towards a general ban on cellulose acetate cigarette filters in the European Union.

After the establishment of a causal relationship between tobacco use and cancer in the 1950s, cellulose acetate filters were introduced with the claim to reduce the adverse health impact of unfiltered cigarettes. Often perceived to be more pleasant and healthy, filters encouraged smoking. However, filtered cigarettes are more deeply inhaled to obtain the same nicotine demand while altered combustion releases more tobacco-specific nitrosamines. The increasing use of cigarette filter ventilation is associated with a sharp rise in lung adenocarcinomas in recent decades. While not preventing adverse health effects, a global environmental problem has been created due to the non-biodegradable filter litter, causing ecotoxicological effects and the spread of microplastics. Recently, the Belgian Superior Health Council advised policymakers to ban cigarette filters as single-use plastics at both national and European levels. This article outlines the arguments used to justify this plea (human health and environment), the expected effects of a filter ban, as well as the public reception and reactions of the tobacco industry. The specific context of the European Union is discussed including the revision of the Single-Use Plastics Directive, affording a new opportunity to ban plastic filters. This perspective article aims to fuel the momentum and cooperation among member states for this purpose.

High molecular weight poly(butylene succinate-co-butylene furandicarboxylate) copolyesters: from catalyzed polycondensation reaction to thermomechanical properties.

Novel potentially biobased aliphatic-aromatic copolyesters poly(butylene succinate-co-butylene furandicarboxylate) (PBSFs) in full composition range were successfully synthesized from 2,5-furandicarboxylic acid (FA), succinic acid (SA), and 1,4-butanediol (BDO) via an esterification and polycondensation process using tetrabutyl titanate (TBT) or TBT/La(acac)(3) as catalyst. The copolyesters were characterized by size exclusion chromatography (SEC), Fourier transform infrared (FTIR), (1)H NMR, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and their tensile properties were also evaluated. The weight average molecular weight (M(w)) ranges from 39,000 to 89,000 g/mol. The copolyesters are random copolymers whose composition is well controlled by the feed ratio of the diacid monomers. PBSFs have excellent thermal stability. The glass transition temperature (T(g)) increases continuously with φ(BF) and agrees well with the Fox equation. The crystallizability and T(m) decrease with increasing butylene furandicarboxylate (BF) unit content (φ(BF)) from 0 to 40 mol %, but rise again at φ(BF) of 50-100 mol %. Consequently, the tensile modulus and strength decrease, and the elongation at break increases with φ(BF) in the range of 0-40 mol %. At higher φ(BF), the modulus and strength increase and the ultimate elongation decreases. Thus, depending on φ(BF), the structure and properties of PBSFs can be tuned ranging from crystalline polymers possessing good tensile modulus (360-1800 MPa) and strength (20-35 MPa) to nearly amorphous polymer of low T(g) and high elongation (~600%), and therefore they may find applications in thermoplastics as well as elastomers or impact modifiers.

Proof of concept of a predictive model of drug release from long-acting implants obtained by fused-deposition modeling.

In the pharmaceutical field, there is a growing interest in manufacturing of drug delivery dosage forms adapted to the needs of a large variety of patients. 3D printing has proven to be a powerful tool allowing the adaptation of immediate drug delivery dosage forms. However, there are still few studies focusing on the adaptation of long-acting dosage forms for patient suffering of neurological diseases. In this study, paliperidone palmitate (PP) was chosen as a model drug in combination with different polymers adapted for fused-deposition modeling (FDM). The impact of different printing parameters on the release of PP were investigated. The layer thickness and the infill percentage were studied using a quality by design approach. Indeed, by defining the critical quality attributes (CQA), a proof of concept of a prediction system, and a quality control system were studied through designs of experiments (DoE). The first part of this study was dedicated to the release of PP from a fix geometry. In the second part, the prediction system was developed to require only surface and surface to volume ratio. From that point, it was possible to get rid of a fix geometry and predict the amount of PP released from complex architectures.

Nanocluster-Based Drug Delivery and Theranostic Systems: Towards Cancer Therapy.

Over the last decades, the global life expectancy of the population has increased, and so, consequently, has the risk of cancer development. Despite the improvement in cancer therapies (e.g., drug delivery systems (DDS) and theranostics), in many cases recurrence continues to be a challenging issue. In this matter, the development of nanotechnology has led to an array of possibilities for cancer treatment. One of the most promising therapies focuses on the assembly of hierarchical structures in the form of nanoclusters, as this approach involves preparing individual building blocks while avoiding handling toxic chemicals in the presence of biomolecules. This review aims at presenting an overview of the major advances made in developing nanoclusters based on polymeric nanoparticles (PNPs) and/or inorganic NPs. The preparation methods and the features of the NPs used in the construction of the nanoclusters were described. Afterwards, the design, fabrication and properties of the two main classes of nanoclusters, namely noble-metal nanoclusters and hybrid (i.e., hetero) nanoclusters and their mode of action in cancer therapy, were summarized.

Green Topochemical Esterification Effects on the Supramolecular Structure of Chitin Nanocrystals: Implications for Highly Stable Pickering Emulsions.

In nature, chitin is organized in hierarchical structures composed of nanoscale building blocks that show outstanding mechanical and optical properties attractive for nanomaterial design. For applications that benefit from a maximized interface such as nanocomposites and Pickering emulsions, individualized chitin nanocrystals (ChNCs) are of interest. However, when extracted in water suspension, their individualization is affected by ChNC self-assembly, requiring a large amount of water (above 90%) for ChNC transport and stock, which limits their widespread use. To master their individualization upon drying and after regeneration, we herein report a waterborne topochemical one-pot acid hydrolysis/Fischer esterification to extract ChNCs from chitin and simultaneously decorate their surface with lactate or butyrate moieties. Controlled reaction conditions were designed to obtain nanocrystals of a comparable aspect ratio of about 30 and a degree of modification of about 30% of the ChNC surface, under the rationale to assess the only effect of the topochemistry on ChNC supramolecular organization. The rheological analysis coupled with polarized light imaging shows how the nematic structuring is hindered by both surface ester moieties. The increased viscosity and elasticity of the modified ChNC colloids indicate a gel-like phase, where typical ChNC clusters of liquid crystalline phases are disrupted. Pickering emulsions have been prepared from lyophilized nanocrystals as a proof of concept. Our results demonstrate that only the emulsions stabilized by the modified ChNCs have excellent stability over time, highlighting that their individualization can be regenerated from the dry state.