RESUMEN
High quantum yield polysaccharide-based materials are significative for the dynamic anti-counterfeiting, while that are limited by weak fluorescence. However, natural polysaccharides with weak fluorescence are not suitable for anti-counterfeiting. Herein, alginate derivatives (SA-PBA) exhibiting aggregation-induced emission with high-quantum yields were synthesized by grafting phenylboronic acid (PBA) onto a sodium alginate (SA) chain. As the concentration increases, polymer assembly can be induced to form more compact soft colloidal aggregates, which enhances the fluorescence properties of alginate derivatives by introducing B â N coordination bonds in the hydrophobic microregions. Interestingly, the clustered aggregates of SA-PBA can be dynamically controlled by pH, realizing the reversible adjustment of fluorescence. The corresponding mechanism is revealed by the combination of coarse-grained simulations and experiments. It is found that SA-PBA uses a hydrophobic driving force and hydrogen bond interaction to self-assemble in an aqueous solution and promote fluorescence emission. Moreover, the fluorescence quantum yield of SA-PBA can reach 14.4 % and can be reversibly altered by tuning soft colloidal microstructures. Therefore, a reversible information encryption system of SA-PBA is developed for anti-counterfeiting. This work shed some light on how to design novel anti-counterfeit materials based on natural polysaccharides and optimize the dynamic fluorescence conditions.
RESUMEN
Significant challenges remain in designing sufficient viscoelasticity polysaccharide-based high internal phase Pickering emulsions (HIPPEs) as soft materials for 3D printing. Herein, taking advantage of the interfacial covalent bond interaction between modified alginate (Ugi-OA) dissolved in the aqueous phase and aminated silica nanoparticles (ASNs) dispersed in oil, HIPPEs with printability were obtained. Using multitechniques coupling a conventional rheometer with a quartz crystal microbalance with dissipation monitoring, the correlation between interfacial recognition coassembly on the molecular scale and the stability of whole bulk HIPPEs on the macroscopic scale can be clarified. The results showed that Ugi-OA/ASNs assemblies (NPSs) were strongly retargeted into the oil-water interface due to the specific Schiff base-binding between ASNs and Ugi-OA, further forming thicker and more rigid interfacial films on the microscopic scale compared with that of the Ugi-OA/SNs (bared silica nanoparticles) system. Meanwhile, flexible polysaccharides also formed a 3D network that suppressed the motion of the droplets and particles in the continuous phase, endowing the emulsion with appropriately viscoelasticity to manufacture a sophisticated "snowflake" architecture. In addition, this study opens a novel pathway for the construction of structured all-liquid systems by introducing an interfacial covalent recognition-mediated coassembly strategy, showing promising applications.
RESUMEN
Functional Pickering emulsions that depend on the interparticle interactions hold promise for building template materials. A novel coumarin-grafting alginate-based amphiphilic telechelic macromolecules (ATMs) undergoing photo-dimerization enhanced particle-particle interactions and changed the self-assembly behavior in solutions. The influence of self-organization of polymeric particles on the droplet size, microtopography, interfacial adsorption and viscoelasticity of Pickering emulsions were further determined by multi-scale methodology. Results showed that stronger attractive interparticle interactions of ATMs (post-UV) endowed Pickering emulsion with small droplet size (16.8 µm), low interfacial tension (9.31 mN/m), thick interfacial film, high interfacial viscoelasticity and adsorption mass, and well stability. The high yield stress, outstanding extrudability (n1 < 1), high structure maintainability, and well shape retention ability, makes them ideal inks for direct 3D printing without any additions. The ATMs provides an increased capacity to produce stable Pickering emulsions with tailoring their interfacial performances and, providing a platform for fabricating and developing alginate-based Pickering emulsion-templated materials.
RESUMEN
Polysaccharide-based soft colloidal particles mediated by the dynamic bonding-engineered interfacial self-assembly can regulate the properties of oil-water interfacial films, availing the stability of emulsions under a wide pH range. The amphiphilic phenylboronic alginate soft colloidal particles (Alg-PBA) were designed to stabilize pH-responsive Pickering emulsions (PEs). Combining stability analysis with quartz crystal microbalance and dissipation monitoring (QCM-D), the microstructure and viscoelasticity of Alg-PBA at the oil-water interface were determined. The results showed that PEs stabilized by Alg-PBA due to a thicker and stronger viscoelastic interface film induced by BO bonds and hydrogen bonds. The structure-function relationship of the Alg-PBA emulsifier driven by dynamic bonds was further elaborated at multiple scales by laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Meanwhile, the microstructure of aerogels templated by emulsion could be tuned by adjusting dynamic bonds, which provides a new idea for polysaccharide soft material engineering.