B ← N coordination bond reinforced dynamic fluorescence of pH-responsive amphiphile alginate aggregates for anti-counterfeiting.

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.

Light-adjusted supramolecular host-guest interfacial recognition for reconfiguring soft colloidal aggregates.

The soft interfacial template-assisted confined self-assembly of block copolymers (BCPs) guiding colloidal aggregates has been extensively investigated by interfacial instability. Whether the macromolecular polymer architectonics possessed stimulus-responsive self-regulated structural controllability more readily implement the morphological diversity of colloidal aggregates. Herein, we in-situ constructed the alginate-modified ß-cyclodextrin/azobenzene-functionalized alkyl chains (Alg-ß-CD/AzoC12) system by supramolecular host-guest interfacial recognition-engineered strategy, in which possessed photo-stimulated responsive structural reconfigurability by modulating assembly/disassembly behaviors between CD and Azo at oil/water interface. The host-guest droplet interfaces acted as soft templates managing interfacial instability by synergistically integrating supra-amphiphilic host-guest polymers with cosurfactants, further constructing various soft supracolloidal aggregates, including soft nanoaggregates, microspheres with tunable degrees of surface roughness. Additionally, the stimuli-altering structural reconfigurability of supramolecular host-guest polymers was regulated by ultraviolet/visible irradiation, endowing soft aggregates with structural diversity. It's highly anticipated that the supramolecular host-guest interfacial recognition self-assembly establishes great bridge between supramolecular host-guest chemistry and colloid interface science.

Light-dimerization telechelic alginate-based amphiphiles reinforced Pickering emulsion for 3D printing.

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.

Coexistence of aggregates and flat states of hydrophobically modified sodium alginate at an oil/water interface: A molecular dynamics study.

Hydrophobically modified sodium alginate stabilizes benzene in water emulsions. The stability of the emulsion is related to the interface properties at the mesoscopic scale, but the details of the polymer adsorption, conformation and organization at oil/water interfaces at the microscopic scale remain largely elusive. In this study, hydrophobically modified sodium alginate was used as a representative of amphiphilic polymers for prediction of distribution of HMSA at the oil/water interface by coarse-grained molecular dynamics simulation. The result showed that driven by the interaction energy between the hydrophobic segment and benzene, HMSA will actively accumulate at the oil/water interface. The HMSA molecules parallel to the oil/water interface prevent the hydrophobic segments in the micelles from approaching the oil/water interface, so that the micelles can exist stably by steric hindrance. This study would be helpful to understand the aggregation behavior of amphiphilic polymers at the oil/water interface, these results can have applications in diverse sectors such as drug, food industry, where polymers are used to stabilize emulsions.

Fabricating Network-Link Acetamiprid-Loading Micelles Based on Dopamine-Functionalized Alginate and Alkyl Polyglucoside To Enhance Folia Deposition and Retention.

The development of an eco-friendly nanopesticide formulation can alleviate the problems of low pesticide utilization and environmental pollution. However, the development of green nanopesticide carriers with ideal physical properties and specific bioavailability is still a challenging task at present. In this study, we propose a novel binary additive pesticide carrier system that is a functional polysaccharide-based polymer/surfactant (Alg-DA/APG) to improve the deposition and retention of pesticide droplets. The self-assembled micelle morphology of Alg-DA/APG and its effect on the apparent viscosity were investigated by transmission electron microscopy (TEM) and a Discovery HR-2 rotational rheometer. Surface tension was carried out to investigate the surface activity and critical micelle concentration (CMC) of Alg-DA/APG. The drop impacting experiments exhibited superior antisplash performance of Alg-DA/APG. Furthermore, a binary additive was used as the carrier material and loaded acetamiprid to prepare nanopesticide formulation Ace@Alg-DA/APG. The encapsulation efficiency (EE) and acetamiprid release behavior from Ace@Alg-DA/APG were also studied. Moreover, the dynamic contact angle (DCA) and retention experiment showed that the DCA and wetting radius at 600 s were, respectively, 6.8 ± 2.39° and 4.044 ± 0.0662 mm for the Ace@0.05 wt % Alg-DA/0.05 wt % APG on the banana foliage surface, and its retention rates on foliage surface were up to 74.80% after washing. The novel binary additive as a nanopesticide carrier has the potential to alleviate the problems of low pesticide utilization and environmental pollution in the future.

Enhancing soil aggregation and acetamiprid adsorption by ecofriendly polysaccharides hydrogel based on Ca2+- amphiphilic sodium alginate.

Soil aggregation plays an important role in agricultural production activities. However, the structure of soil aggregation is destroyed by the natural environment and unreasonable farming management, resulting in the loss of water, fertilizers and pesticides in soil. At present, hydrogels have been widely reported to promote the formation of soil aggregation. In this paper, amphiphilic calcium alginate (ASA/Ca2+) was applied to promote the formation of soil aggregation and enhance pesticide retention. Initially, an ASA was obtained through the one-pot Ugi condensation (a four-component green chemical reaction). Then, ASA/Ca2+ hydrogel is prepared by Ca2+ cross-linking. The formation of soil aggregation was determined through the Turbiscan Lab Expert stability analyzer, Confocal Laser Scanning Microscope (CLSM), and Transmission Electron Microscope (TEM). And the effect of soil aggregation on acetamiprid environmental behavior was investigated by adsorption kinetics, adsorption isotherms, and leaching. The results shown that the three-dimensional network structure of ASA/Ca2+ hydrogel can promote the formation of soil aggregation. Aggregate durability index (ADI) was 0.55 in the presence of ASA/Ca2+ hydrogel, indicating that amphiphilic hydrogel can enhance the stability of soil aggregation. The adsorbing capacity of acetamiprid was 1.58 times higher than pure soil, and the release of acetamiprid only about 20% in the presence of ASA/Ca2+ hydrogel. These results would be helpful for the formation of soil aggregation and pesticides adsorption on soil aggregation. Thus, ASA/Ca2+ hydrogel is likely to improve soil quality, simultaneously it can minimize the mobility of pesticides in the agricultural system.

Tuning Supramolecular Polymers' Amphiphilicity via Host-Guest Interfacial Recognition for Stabilizing Multiple Pickering Emulsions.

Supramolecular host-guest chemistry bridging the adjustable amphiphilicity and macromolecular self-assembly is well advanced in aqueous media. However, the interfacial self-assembled behaviors have not been further exploited. Herein, we designed a ß-cyclodextrin-grafted alginate/azobenzene-functionalized dodecyl (Alg-ß-CD/AzoC12) supra-amphiphilic system that possessed tunable amphiphilicity by host-guest interfacial self-assembly. Especially, supra-amphiphilic aggregates could be utilized as highly efficient soft colloidal emulsifiers for stabilizing water-in-oil-water (W/O/W) Pickering emulsions due to the excellent interfacial activity. Meanwhile, the assembled particle structures could be modulated by adjusting the oil-water ratio, resulting from the tunable aggregation behavior of supra-amphiphilic macromolecules. Additionally, the interfacial adsorption films could be partially destroyed/reconstructed upon ultraviolet/visible irradiation due to the stimuli-altering balance of amphiphilicity of Alg-ß-CD/AzoC12 polymers, further constructing the stimulus-responsive Pickering emulsions. Therefore, the supramolecular interfacial self-assembly-mediated approach not only technologically advances the continued development of creative templates to construct multifunctional soft materials with anisotropic structures but also serves as a creative bridge between supramolecular host-guest chemistry, colloidal interface science, and soft material technology.

High-viscosity Pickering emulsion stabilized by amphiphilic alginate/SiO2 via multiscale methodology for crude oil-spill remediation.

The separation of crude oil from oily water and collection of the emulsion constituents has attracted significant attention. We demonstrate that the relationships between inherent dynamic factors and the performance of a Pickering emulsion stabilized by SiO2 particles with adsorbed hydrophobically modified sodium alginate derivatives (HMSA), a natural pH-sensitive polysaccharide, can be clarified via a multi-scale methodology. Functionalization of the silica surface with HMSA controls particle dispersibility, as verified by turbidity and stability analyses, the zeta potential, and transmission electron microscopy measurements. The interaction mechanism between HMSA and SiO2 nanoparticles was elucidated by both experimental adsorption measurements and computer simulations, which showed qualitative consistency. The aggregation/disaggregation of HMSA/SiO2 particles achieved by tuning the pH of the solution facilitated reversible dispersibility/collectability behavior. Overall, a high-viscosity Pickering emulsion system based on particle-particle and droplet-droplet interactions, which can be filtered for the recovery of spilled crude oil, was demonstrated.

Interfacial self-assembled behavior of pH/light-responsive host-guest alginate-based supra-amphiphiles for controlling emulsifying property.

Soft emulsifiers with relatively suitable structural controllability are necessarily required for the preparation of multifunctional Pickering emulsions. Herein, a ß-cyclodextrin-grafted alginate/azobenzene-functionalized dodecyl (Alg-ß-CD/AzoC. 12) polymeric supra-amphiphile was designed based on the host-guest interfacial self-assembly. As compared with Alg-ß-CD amphiphilic polymers, the interfacial tension of Alg-ß-CD/AzoC12 supra-amphiphilic assemblies reduced from 29.57 mN/m to 0.18 mN/m, indicating the great amphiphilicity derived from Alg-ß-CD/AzoC12 supra-amphiphilic assemblies. With the increase of pH, the interfacial microstructures transformed from flocculated structures, spherical structures into deformed structures. Especially, the spherical microstructures with the highest interfacial viscoelasticity and thickness demonstrated the highest emulsifying efficiency due to the steric hindrance mechanism. Moreover, the interfacial elastic modulus of adsorbed layers exhibited ~4 times of that upon the ultraviolet illumination. These results disclosed that the interfacial microstructures could be readily regulated by the tunable amphiphilicity of Alg-ß-CD/AzoC12 assemblies, which would be useful for the applications of Pickering emulsions in numerous fields.

Highly stretchable and tough alginate-based cyclodextrin/Azo-polyacrylamide interpenetrating network hydrogel with self-healing properties.

Most structural self-healing materials were developed based on either reversible supramolecular interaction or dynamic covalent bonding. It seems a good idea to incorporate self-healing properties into high-performance materials. In this study, we fabricated the alginate-based cyclodextrin and polyacrylamide azobenzene highly stretchable and tough interpenetrating composite hydrogel with self-repairing behavior under light irradiation. Initially, the alginate-based cyclodextrin and polyacrylamide azobenzene were designed and synthesized. The corresponding structural, thermal, and morphological properties of hydrogels were characterized. The reversible transformation of the sol-gel can be achieved by the irradiation upon ultraviolet light and visible light. The self-healing behavior of this composited gel is based on the host-guest interaction between cyclodextrin and azobenzene. The recovery gel elongation at 48 h healing in the dark condition was is 0.04 MPa, with an elongation of 1140 %. Therefore, this gel can achieve self-healing ability while maintaining highly stretchable and tough performance.

Self-aggregation behavior of hydrophobic sodium alginate derivatives in aqueous solution and their application in the nanoencapsulation of acetamiprid.

In this study, cholesteryl-grafted sodium alginate derivatives (CSAD) with different molecular weights were synthesized by esterification. The structure of CSAD was confirmed by FT-IR and 1H NMR spectrometers. The effects of pH and CSAD polymer concentration on the self-assembled behavior and particle size of CSAD were investigated by fluorescence measurement (FM) and dynamic light scattering (DLS). In the presence of Ca2+, the cholesteryl-grafted sodium alginate derivative was used for fabricating self-assembled nanoparticles that can effectively encapsulate the drug acetamiprid. The drug-loaded nanoparticles were characterized by transmission electron microscopy (TEM). The encapsulation efficiency (EE) and acetamiprid drug release behavior from the nanoparticles were also studied. The results reveal that CSAD self-assembled nanoparticles had a diameter of 100nm and were nonaggregated in aqueous media; Moreover, the encapsulation efficiency and the release behavior of nanoparticles were influenced by the MW of CSAD. The mechanism of acetamiprid release was found to vary from non-Fickian (anomalous) to Fickian transport with a decrease in the molecular weight of CSAD.

A pH-responsive emulsion stabilized by alginate-grafted anisotropic silica and its application in the controlled release of λ-cyhalothrin.

Alginate (Alg) was grafted on the surface of anisotropic silica (SiO2-x) via the Ugi reaction (Alg-SiO2-1, Alg-SiO2-2, and Alg-SiO2-4). Compared with pristine SiO2-x, modified SiO2-x is more sensitive to pH. Three stable liquid paraffin-in-water emulsions were prepared with Alg-SiO2-1, Alg-SiO2-2, and Alg-SiO2-4. Alg-SiO2-2 exhibited satisfactory emulsification ability. The emulsions became more stable as emulsion pH varied from 2.0 to 6.2 because of polymer chain interactions that led to the formation of a three-dimensional network. When the emulsion pH varied from 6.2 to 8.0, the particle charge increased, in turn increasing interparticle the electrostatic interactions that increased emulsion stability. When the emulsion pH was 9.0, the subsequent decrease in particle charge, decreased the emulsion stability. The model drug λ-cyhalothrin was embedded in the emulsions. A sustained-release assay demonstrated that increasing emulsion pH from 3.0 to 8.0 decreased cumulative drug release from the emulsion from 99.7% to 13.5%. This result indicated that the emulsion is a pH triggered drug delivery system. The sustained-release curves of λ-cyhalothrin are describable by the Weibull model.

Structural and rheological characterizations of nanoparticles of environment-sensitive hydrophobic alginate in aqueous solution.

Amphiphilic polymers that form self-assembled structures in aqueous media have been investigated and used for the diagnosis and therapy of various diseases, including cancer. In our work, a series of environment-sensitive hydrophobic alginates (Ugi-Alg) with various weight-average molecular mass values (Mw~6.7×105-6.7×104g/mol) were synthesized via Ugi reaction. The structure of Ugi-Alg was characterized by 1HNMR spectrometer. The electrostatic self-assembly of different molecular weight (Mw) and composition (M/G ratio) of Ugi-Alg chain under various Na+ concentrations, was investigated by dynamic light scattering, electron spin resonance experiments, and transmission electron microscopy. Result showed that by comparing to other Ugi-Alg, the mid-Mw Ugi-Alg (Mw~2.8×105g/mol) could form stable and homogeneous nanoparticles in low Na+ concentration solution. However, G/M values exerted no obvious effect on nanoparticles structure. Additionally, steady-shear flow, thixotropy and dynamical viscoelasticity tests were performed to characterize the rheological behavior of Ugi-Alg aqueous solutions as influenced by Mw and M/G ratio. All of the samples exhibited a non-Newtonian shear-thinning behavior above a critical shear rate (γ̇c2). The greater the Mw, the more sensitive the temperature-dependent behavior will be. The upward-downward rheograms showed that all of the systems evaluated in this study displayed a hysteresis loop, indicating a strong thixotropic behavior, and the thixotropic of mid-Mw Ugi-Alg was the strongest. The dynamical viscoelastic properties were characterized by oscillatory frequency sweep, revealing the gel-like viscoelastic behavior of mid-low Ugi-Alg and the fluid-like viscoelastic behavior of high-Mw Ugi-Alg.