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1.
Int J Biol Macromol ; : 133504, 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38944069

RESUMO

We study the effect of electrolytes on the stability in aqueous media of spherical lignin particles (LP) and its relevance to Pickering emulsion stabilization. Factors considered included the role of ionic strength on morphology development, LP size distribution, surface charge, interfacial adsorption, colloidal and wetting behaviors. Stable emulsions are formed at salt concentrations as low as 50 mM, with the highest stability observed at a critical concentration (400 mM). We show salt-induced destabilization of LP aqueous dispersions at an ionic strength >400 mM. At this critical concentration LP flocculation takes place and particulate networks are formed. This has a profound consequence on the stability of LP-stabilized Pickering emulsions, affecting rheology and long-term stability. The results along with quartz microgravimetry and confocal microscopy observations suggest a possible mechanism for stabilization that considers the interfacial adsorption of LP at oil/water interfaces. The often-unwanted colloidal LP destabilization in water ensues remarkably stable Pickering emulsions by the effect of network formation.

2.
Chem Soc Rev ; 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38864385

RESUMO

Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences.

3.
Carbohydr Polym ; 340: 122299, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38858022

RESUMO

As integral parts of fuel cells, polymer electrolyte membranes (PEM) facilitate the conversion of hydrogen's chemical energy into electricity and water. Unfortunately, commercial PEMs are associated with high costs, limited durability, variable electrochemical performance and are based on perfluorinated polymers that persist in the environment. Nanocellulose-based PEMs have emerged as alternative options given their renewability, thermal and mechanical stability, low-cost, and hydrophilicity. These PEMs take advantage of the anionic nature of most nanocelluloses, as well as their facile modification with conductive functional groups, for instance, to endow ionic and electron conductivity. Herein, we incorporated for the first time two nanocellulose types, TEMPO-oxidized and sulfonated, to produce a fully bio-based PEM and studied their contribution separately and when mixed in a PEM matrix. Sulfonated nanocellulose-based PEMs are shown to perform similarly to commercial and bio-based membranes, demonstrating good thermal-oxidative stability (up to 190 °C), mechanical robustness (Young's modulus as high as 1.15 GPa and storage moduli >13 GPa), and high moisture-uptake capacity (ca. 6330 % after 48 h). The introduced nanocellulose membranes are shown as promising materials for proton-exchange material applications, as required in fuel cells.

4.
Carbohydr Polym ; 339: 122242, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38823911

RESUMO

Glucuronoxylans (GX), particularly crude fractions obtained by pressurized hot water extraction of birch wood, act as potent emulsifiers and stabilizers against physical separation and lipid oxidation. Herein, we studied the adsorption of GX on hydrophobic interfaces to correlate their multicomponent character towards the formation of interfacial layers in emulsions. Dynamic interfacial tension (DIFT) and quartz crystal microgravimetry with dissipation monitoring (QCM-D) were applied to various GX fractions and the results compared with those from cellulose-based emulsifiers. The roles of residual lignin and polysaccharides are discussed considering the formation of interfacial layers during emulsification. The DIFT of the different GXs reached quasi-equilibrium faster as the lignin concentration increased, implying a correlation between the rate of adsorption and the residual lignin content. The effect of NaCl addition was more pronounced in polysaccharide-rich fractions, indicating that the polysaccharide fraction modulated the effect of ionic strength. QCM-D showed that despite the fast adsorption exhibited by the lignin-rich GX extract in the DIFT curves, the adsorbed materials were lightweight, suggesting that the polysaccharide fraction built the bulk of the interfacial layer. These results provide a foundation towards understanding the role of GX in interfacial stabilization beyond traditional plant-based counterparts.

5.
Carbohydr Polym ; 341: 122341, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38876727

RESUMO

This study elucidates the intricate interactions between chitin nanocrystals (ChNC) and surfactants of same hydrophobic tail (C12) but different head groups types (anionic, cationic, nonionic): sodium dodecyl sulfate (SDS), dodecyltrimethylammonium bromide (DTAB), and polyoxyethylene(23)lauryl ether (Brij-35). Isothermal Titration Calorimetry (ITC) and rheology are used to study the complex ChNC-surfactant interactions in aqueous media, affected by adsorption, self-assembly and micellization. The ITC results demonstrate that the surfactant head group significantly influences the dynamics and nature of the involved phenomena. Cationic DTAB's reveal minimal interaction with ChNC, non-ionic Brij-25's interact moderately at low concentrations driven by hydrophobic effects while SDS's interacts strongly and show complex interaction patterns that fall across four distinct regimes with SDS addition. We attribute such behavior to initiate through electrostatic attraction and terminate in surfactant micelle formation on ChNC surfaces. ITC also elucidates the impact of ChNC concentration on key parameters including critical aggregation concentration (CAC) and saturation concentration (C2). Dynamic rheological analysis indicates the molecular interactions translate to non-linear variations in the elastic modulus (G') upon SDS addition mirroring that observed in ITC experiments. Such a direct correlation between molecular interactions and macroscopic rheological properties provides insights to aid in the creation of nanocomposites with tailored properties.

6.
Nanoscale ; 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38881312

RESUMO

Bio-based functional materials can be used to replace or limit the use of synthetic materials sourced from unsustainable sources. However, the potential of such materials remains largely unexplored. In this study, we demonstrate the use of weak AC electric fields to deposit ultra-thin piezoelectric films from cellulose nanocrystals (CNC). This is the first time electric fields are used to realize <50 nm thick uniform bio-based piezoelectric films wherein the bioparticles exhibit unidirectional arrangement. Interestingly, we found that the use of weak AC electric fields of suitable frequencies completely mitigates the coffee ring effect (CRE), which results in defect-free uniform ultra-thin films. Additionally, the electric fields appear to help in realizing unidirectional alignment of particles in the films, which enhances their piezoelectric properties. The method was also tested for chitin nanocrystals (ChNC), which have a similar aspect ratio but bear opposite polarity surface charges, and the influence of the field on coffee ring formation and particle orientation in CNC thin film deposition was validated. The phenomena can be attributed to the constant spatio-temporal curvature of the evaporating liquid film, the transient state between the three-phase contact (TPC) line, the electric field-dependent contact angle, and the permanent and field-induced dipole moments. These factors lead to particle polarization and alignment. The films have an optimum electrical frequency of deposition at which they are continuous and uniformly thin, have unidirectional alignment of particles, and function as a single dipole.

7.
Polymers (Basel) ; 16(11)2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38891529

RESUMO

We developed a highly sensitive solid-state sensor for mercury detection by stabilizing red-sub-nanometric fluorescent gold nanoclusters (AuNC, 0.9 ± 0.1 nm diameter) with bovine serum albumin in a matrix composed of cellulose nanofibrils (CNF) (BSA-AuNC/CNF). The main morphological and optical features of the system were investigated via atomic force/transmission electron microscopy and UV-Vis/fluorescence spectroscopy. The hybrid film (off-white and highly transparent) showed strong photoluminescene under UV irradiation. The latter is assigned to the AuNC, which also increase the ductility of the emitting film, which was demonstrated for high sensitivity Hg2+ detection. When used as a sensor system, following AuNC printing on CNF hybrid films, a limit of detection <10 nM was confirmed. What is more, nanocellulose films have a high pore structure and selective separation properties, showcasing a wide range of potential applications in many fields such as water treatment and oil-water separation.

8.
ACS Nano ; 18(23): 14954-14967, 2024 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-38820368

RESUMO

Chitin nanofibrils (ChNF) sourced from discarded marine biomass are shown as effective stabilizers of carbon nanomaterials in aqueous media. Such stabilization is evaluated for carbon nanotubes (CNT) considering spatial and temporal perspectives by using experimental (small-angle X-ray scattering, among others) and theoretical (atomistic simulation) approaches. We reveal that the coassembly of ChNF and CNT is governed by hydrophobic interactions, while electrostatic repulsion drives the colloidal stabilization of the hybrid ChNF/CNT system. Related effects are found to be transferable to multiwalled carbon nanotubes and graphene nanosheets. The observations explain the functionality of hybrid membranes obtained by aqueous phase processing, which benefit from an excellent areal mass distribution (correlated to piezoresistivity), also contributing to high electromechanical performance. The water resistance and flexibility of the ChNF/CNT membranes (along with its tensile strength at break of 190 MPa, conductivity of up to 426 S/cm, and piezoresistivity and light absorption properties) are conveniently combined in a device demonstration, a sunlight water evaporator. The latter is shown to present a high evaporation rate (as high as 1.425 kg water m-2 h-1 under one sun illumination) and recyclability.

9.
Nanoscale Horiz ; 9(7): 1155-1165, 2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38747281

RESUMO

This study introduces a new, facile method to synthesize silver clusters from aqueous silver ion solution by using high intensity femtosecond pulse laser irradiation. The particles obtained in the absence of reducing or capping agents are 1-17 nm in size and presented quantum properties, as characterized by fluorescence, but did not exhibit plasmon signals, which is not a common characteristic of conventional silver nanoparticles. In a further development, small silver quantum clusters (∼1 nm) were bound in situ to wet-spun filaments of cellulose nanofibrils by pulsed laser irradiation. The obtained hybrid filaments as well as free silver quantum clusters revealed a catalytic activity remarkably higher than that of free gold quantum clusters; moreover, the hybrid filaments were found to show improved stability and cycling performance for silver-based catalysis. The present results indicate the potential of femtosecond laser irradiation to generate clusters as well as hybrid systems with excellent performance and reactivity.

10.
ACS Appl Mater Interfaces ; 16(17): 22532-22546, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38629598

RESUMO

Electroactive filament electrodes were synthesized by wet-spinning of cellulose nanofibrils (CNF) followed by femtosecond pulse laser deposition of ZnO (CNF@ZnO). A layer of conducting conjugated polymers was further adsorbed by in situ polymerization of either pyrrole or aniline, yielding systems optimized for electron conduction. The resultant hybrid filaments were thoroughly characterized by imaging, spectroscopy, electrochemical impedance, and small- and wide-angle X-ray scattering. For the filaments using polyaniline, the measured conductivity was a result of the synergy between the inorganic and organic layers, while the contribution was additive in the case of the systems containing polypyrrole. This observation is rationalized by the occurrence of charge transfer between ZnO and polyaniline but not that with polypyrrole. The introduced conductive hybrid filaments displayed a performance that competes with that of metallic counterparts, offering great promise for next-generation filament electrodes based on renewable nanocellulose.

11.
Small ; : e2309756, 2024 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-38602191

RESUMO

Control over particle size and shape heterogeneity is highly relevant to the design of photonic coatings and supracolloidal assemblies. Most developments in the area have relied on mineral and petroleum-derived polymers that achieve well-defined chemical and dimensional characteristics. Unfortunately, it is challenging to attain such control when considering renewable nanoparticles. Herein, a pathway toward selectable biobased particle size and physicochemical profiles is proposed. Specifically, lignin is fractionated, a widely available heterogeneous polymer that can be dissolved in aqueous solution, to obtain a variety of monodispersed particle fractions. A two-stage cascade and density gradient centrifugation that relieves the need for solvent pre-extraction or other pretreatments but achieves particle bins of uniform size (~60 to 860 nm and polydispersity, PDI<0.06, dynamic light scattering) along with characteristic surface chemical features is introduced. It is found that the properties and associated colloidal behavior of the particles are suitably classified in distinctive size populations, namely, i) nanoscale (50-100 nm), ii) photonic (100-300 nm) and iii) near-micron (300-1000 nm). The strong correlation that exists between size and physicochemical characteristics (molar mass, surface charge, bonding and functional groups, among others) is introduced as a powerful pathway to identify nanotechnological uses that benefit from the functionality and cost-effectiveness of biogenic particles.

12.
Carbohydr Polym ; 335: 122059, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38616073

RESUMO

Cellulose-based humidity sensors have attracted great research interest due to their hydrophilicity, biodegradability, and low cost. However, they still suffer from relatively low humidity sensitivity. Due to the presence of negatively charged carboxylate groups, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibril (CNF) exhibits enhanced hydrophilicity and ion conductivity, which is considered a promising candidate for humidity sensing. In this work, we developed a facile strategy to improve the humidity sensitivity of CNF films by regulating their surface charge density. With the increase in surface charge density, both water uptake and charge carrier densities of the CNF films can be improved, enabling a humidity sensitivity of up to 44.5 % (%RH)-1, higher than that of most polymer-based humidity sensors reported in the literature. Meanwhile, the sensor also showed good linearity (R2 = 0.998) over the 15-75 % RH at 1 kHz. With these features, the CNF film was further demonstrated for applications in noncontact sensing, such as human respiration, moisture on fingertips, and water leakage, indicating the great potential of CNF film in humidity monitoring.

13.
Biomacromolecules ; 25(4): 2367-2377, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38456841

RESUMO

Soil quality is one of the main limiting factor in the development of the food sector in arid areas, mainly due to its poor mechanics and lack of water retention. Soil's organic carbon is nearly absent in arid soils, though it is important for water and nutrient transport, to soil mechanics, to prevent erosion, and as a long-term carbon sink. In this study, we evaluate the potential benefits that are brought to inert sand by the incorporation of a range of, mainly, cellulosic networks in their polymeric or structured (fiber) forms, analogously to those found in healthy soils. We explore the impact of a wide range of nonfood polysaccharide-based amendments, including pulp fibers, nanocellulose, cellulose derivatives, and other readily available polysaccharide structures derived from arthropods (chitosan) or fruit peels (pectin) residues. A practical methodology is presented to form sand-polymer composites, which are evaluated for their soil mechanics as a function of humidity and the dynamics of their response to water. The mechanics are correlated to the network of polymers formed within the pores of the sandy soil, as observed by electron microscopy. The response to water is correlated to both the features of the network and the individual polysaccharides' physicochemical features. We expect this work to provide a rapid and reproducible methodology to benchmark sustainable organic amendments for arid soils.


Assuntos
Celulose , Areia , Benchmarking , Umidade , Solo/química , Água/química , Polímeros
14.
Nanoscale ; 16(18): 8858-8867, 2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38488103

RESUMO

For decades, the inherently reflective nature of metallic electromagnetic (EM) shields and their induced secondary EM pollution have posed significant challenges for sensitive electronics. While numerous efforts have been made to develop superior EM shielding systems, the issue of reflection dominancy in metallic substrates remains unresolved. Herein, we addressed this long-lasting obstacle by pairing metallic shields with ultra-lightweight (density of 3.12-3.40 mg cm-3) elastic anti-reflection aerogels, altering their shielding mechanism from dominant reflection (reflectance >0.8) to absorption (absorbance >0.7) by trapping EM waves inside the aerogel. The aerogel EM traps were generated using interfacial complexation, yielding engineerable filamentous liquid structures. These served as templates for aerogel creation through a follow-up process of freezing and lyophilization. The engineerable lossy medium of aerogels benefits from a multi-scale porous construct with the combined action of dielectric and conduction losses, highly dissipating the EM waves and minimizing the reflections. Notably, declining the diameter of aerogel filaments promoted its absorption dominancy, rendering it a potent dissipating medium for EM waves. Pairing a metallic substrate with filamentous aerogel EM traps has resulted in an exceptionally effective absorption-dominant shielding system, achieving absorbance levels between 0.70-0.81. This system offers a shielding effectiveness of 53-89 dB within the X-band frequency range. This innovation addresses a persistent issue in shielding science related to the reflective characteristics of metallic substrates, effectively inhibiting their induced EM reflections.

15.
Carbohydr Polym ; 332: 121877, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38431389

RESUMO

This work aims to understand how nanocellulose (NC) processing can modify the key characteristics of NC films to align with the main requirements for high-performance optoelectronics. The performance of these devices relies heavily on the light transmittance of the substrate, which serves as a mechanical support and optimizes light interactions with the photoactive component. Critical variables that determine the optical and mechanical properties of the films include the morphology of cellulose nanofibrils (CNF), as well as the concentration and turbidity of the respective aqueous suspensions. This study demonstrates that achieving high transparency was possible by reducing the grammage and adjusting the drying temperature through hot pressing. Furthermore, the use of modified CNF, specifically carboxylated CNF, resulted in more transparent films due to a higher nanosized fraction and lower turbidity. The mechanical properties of the films depended on their structure, homogeneity (spatial uniformity of local grammage), and electrokinetic factors, such as the presence of electrostatic charges on CNF. Additionally, we investigated the angle-dependent transmittance of the CNF films, since solar devices usually operate under indirect light. This work demonstrates the importance of a systematic approach to the optimization of cellulose films, providing valuable insight into the optoelectronic field.

16.
Adv Mater ; : e2400311, 2024 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-38483010

RESUMO

The growth of aerobic microbes at air-water interfaces typically leads to biofilm formation. Herein, a fermentative alternative that relies on oil-water interfaces to support bacterial activity and aerotaxis is introduced. The process uses under-liquid biofabrication by structuring bacterial nanocellulose (BNC) to achieve tailorable architectures. Cellulose productivity in static conditions is first evaluated using sets of oil homologues, classified in order of polarity. The oils are shown for their ability to sustain bacterial growth and BNC production according to air transfer and solubilization, both of which impact the physiochemical properties of the produced biofilms. The latter are investigated in terms of their morphological (fibril size and network density), structural (crystallinity) and physical-mechanical (surface area and strength) features. The introduced under-liquid biofabrication is demonstrated for the generation of BNC-based macroscale architectures and compartmentalized soft matter. This can be accomplished following three different routes, namely, 3D under-liquid networking (multi-layer hydrogels/composites), emulsion templating (capsules, emulgels, porous materials), and anisotropic layering (Janus membranes). Overall, the proposed platform combines living matter and multi-phase systems as a robust option for material development with relevance in biomedicine, soft robotics, and bioremediation, among others.

17.
Nat Commun ; 15(1): 2375, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38490985

RESUMO

There is interest in developing sustainable materials displaying circularly polarized room-temperature phosphorescence, which have been scarcely reported. Here, we introduce biobased thin films exhibiting circularly polarized luminescence with simultaneous room-temperature phosphorescence. For this purpose, phosphorescence-active lignosulfonate biomolecules are co-assembled with cellulose nanocrystals in a chiral construct. The lignosulfonate is shown to capture the chirality generated by cellulose nanocrystals within the films, emitting circularly polarized phosphorescence with a 0.21 dissymmetry factor and 103 ms phosphorescence lifetime. By contrast with most organic phosphorescence materials, this chiral-phosphorescent system possesses phosphorescence stability, with no significant recession under extreme chemical environments. Meanwhile, the luminescent films resist water and humid environments but are fully biodegradable (16 days) in soil conditions. The introduced bio-based, environmentally-friendly circularly polarized phosphorescence system is expected to open many opportunities, as demonstrated here for information processing and anti-counterfeiting.

18.
ACS Nano ; 18(11): 7959-7971, 2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38501309

RESUMO

The methods used to date to produce compressible wood foam by top-down approaches generally involve the removal of lignin and hemicelluloses. Herein, we introduce a route to convert solid wood into a super elastic and insulative foam-like material. The process uses sequential oxidation and reduction with partial removal of lignin but high hemicellulose retention (process yield of 72.8%), revealing fibril nanostructures from the wood's cell walls. The elasticity of the material is shown to result from a lamellar structure, which provides reversible shape recovery along the transverse direction at compression strains of up to 60% with no significant axial deformation. The compressibility is readily modulated by the oxidation degree, which changes the crystallinity and mobility of the solid phase around the lumina. The performance of the highly resilient foam-like material is also ascribed to the amorphization of cellulosic fibrils, confirmed by experimental and computational (molecular dynamics) methods that highlight the role of secondary interactions. The foam-like wood is optionally hydrophobized by chemical vapor deposition of short-chained organosilanes, which also provides flame retardancy. Overall, we introduce a foam-like material derived from wood based on multifunctional nanostructures (anisotropically compressible, thermally insulative, hydrophobic, and flame retardant) that are relevant to cushioning, protection, and packaging.

19.
Biomacromolecules ; 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38507559

RESUMO

Cellulose nanocrystals (CNCs) are biobased colloidal nanorods that have unlocked new opportunities in the area of sustainable functional nanomaterials including structural films and coatings, biomedical devices, energy, sensing, and composite materials. While selective light reflection and sensing develop from the typical chiral nematic (cholesteric, Nem*) liquid crystallinity exhibited by CNCs, a wealth of technologies would benefit from a nematic liquid crystal (LC) with CNC uniaxial alignment. Therefore, this study answers the central question of whether surfactant complexation suppresses CNC chirality in favor of nematic lyotropic and thermotropic liquid crystallinity. Therein, we use a common surfactant having both nonionic and anionic blocks, namely, oligo(ethylene glycol) alkyl-3-sulfopropyl diether potassium salt (an alcohol ethoxy sulfonate (AES)). AES forms complexes with CNCs in toluene (a representative for nonpolar organic solvent) via hydrogen bonding with an AES' oligo(ethylene glycol) block. A sufficiently high AES weight fraction endows the dispersibility of CNC in toluene. Lyotropic liquid crystallinity with Schlieren textures containing two- and four-point brush defects is observed in polarized optical microscopy (POM), along with the suppression of the cholesteric fingerprint textures. The results suggest a nematic (Nem) phase in toluene. Moreover, thermotropic liquid crystallinity is observed by incorporating an excess of AES, in the absence of an additional solvent and upon mild heating. The Schlieren textures suggest a nematic system that undergoes uniaxial alignment under mild shear. Importantly, replacing AES with a corresponding nonionic surfactant does not lead to liquid crystalline properties, suggesting electrostatic structural control of the charged end group of AES. Overall, we introduce a new avenue to suppress CNC chirality to achieve nematic structures, which resolves the long-sought uniaxial alignment of CNCs in filaments, composite materials, and optical devices.

20.
Langmuir ; 40(9): 4881-4892, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38386001

RESUMO

Chitin has a unique hierarchical structure, spanning the macro- and nanoscales, and presents chemical characteristics that make it a suitable component of multiphase systems. Herein, we elucidate the colloidal interactions between partially deacetylated chitin nanocrystals (cationic ChNC) and an anionic surfactant, sodium dodecyl sulfate (SDS). We investigate charge neutralization and association (electrophoretic mobility, surface tensiometry, and quartz crystal microgravimetry) and their role in the stabilization of Pickering emulsions. We find SDS adsorption and association with ChNC under distinctive regimes: At low SDS concentration, submonolayer assemblies form on ChNC, driven by the hydrophobic effect and electrostatic interactions. With the increased SDS concentration, bilayers or patchy bilayers form, followed by adsorbed hemimicelles and micelles. We further suggested the role of hydrophobic effects in the observed colloidal transitions and complex conformations. At the highest SDS concentration tested, charge neutralization and SDS/ChNC flocculation take place. Remarkably, at given concentrations, adsorbed SDS endows the chitin nanoparticles with an effective hydrophobicity that opens the opportunity to achieve tailorable Pickering stabilization. Hence, a facile route is proposed by in situ modification by SDS physisorption, which extends the potential of renewable nanoparticles in the formulation of complex fluids, for instance, those relevant to household and healthcare products.

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