Dynamic Covalent Nanoparticles for Acid-Responsive Nonaqueous Pickering Emulsions.

Acid-responsive nonaqueous (glycerol in n-decane) Pickering emulsions were prepared using preferentially oil-wetted dynamic covalent silica (SiO2-pDB) nanoparticles as the Pickering emulsifiers. The acid-responsive Pickering emulsifier SiO2-pDB was prepared based on a Schiff base reaction between amino silica (SiO2-NH2) and p-decanoxybenzaldehyde (pDBA). The formation of SiO2-pDB was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis. The preferentially oil-wetted character of SiO2-pDB was indicated by contact angle measurement. Stable nonaqueous Pickering emulsions were prepared using preferentially oil-wetted SiO2-pDB as the Pickering emulsifier. However, after adjusting the nonaqueous Pickering emulsions to an acidic environment, complete phase separation occurred. In the acidic environment, preferentially oil-wetted SiO2-pDB decomposed into hydrophilic SiO2-NH2 and hydrophobic pDBA due to the decomposition of the dynamic imine bond in the SiO2-pDB. Then, the hydrophilic SiO2-NH2 and hydrophobic pDBA desorbed from the two-phase interface, resulting in complete phase separation of the initially stable nonaqueous Pickering emulsions. The acid-responsive nonaqueous Pickering emulsions show great potential in application in water sensitive systems, such as oil-based drilling fluids.

Temperature and CO2 Dual-Responsive Pickering Emulsions Using Jeffamine M2005-Modified Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) with excellent biodegradability are promising biomaterials for use as responsive Pickering emulsifiers. However, the high hydrophilicity of CNCs limits their emulsification ability. Some existing studies have utilized complicated covalent modification procedures to increase the hydrophobicity of CNCs. To simplify the modification process, we prepared hydrophobically modified CNCs (CNCs-M2005) via simple and controllable electrostatic interactions with thermosensitive M2005. The obtained CNCs-M2005 exhibited temperature and CO2 dual-responsive properties. Subsequently, stable oil/water Pickering emulsions were prepared using the partially hydrophobic CNCs-M2005 at 20 °C. However, demulsification occurred when the temperature increased to 60 °C. This temperature-induced demulsification resulted from the dehydration of polyethylene oxide and polypropylene oxide, causing the aggregation of the CNCs-M2005, as shown by dynamic light scattering and transmission electron microscopy experiments. In addition, demulsification was also achieved after bubbling CO2, which was attributed to the dissociation of the partially hydrophobic CNCs-M2005. The temperature and CO2 dual-responsive biosafe Pickering emulsions open up opportunity for the design of intelligent food, cosmetic, and drug delivery systems.

Dynamic Covalent Silica Nanoparticles for pH-Switchable Pickering Emulsions.

Dynamic covalent surfactants have been recently reported for preparation of pH-switchable emulsions [ Sun , D. Langmuir , 2017 , 33 , 3040 ]. In this study, dynamic covalent silica (SiO2-B) nanoparticles of switchable wettability were fabricated by a pH-responsive dynamic (covalent) imine bond between hydrophilic amino silica (SiO2-NH2) nanoparticles and hydrophobic benzaldehyde molecules. The properties of SiO2-B were characterized by Fourier transform infrared spectroscopy, elemental analysis, contact angle measurement, and ζ potential measurement. The hydrophilicity and hydrophobicity of SiO2-B were shown to be readily switchable by adjusting pH between 7.8 and 3.5. At pH 7.8, SiO2-B was partially hydrophobic and adsorbed at oil-water interface to stabilize O/W Pickering emulsions, which were characterized by electrical conductivity, optical microscopy, and confocal laser scanning microscopy. Upon lowering the pH to 3.5, the dynamic covalent bond is dissociated to convert partially hydrophobic SiO2-B into highly hydrophilic SiO2-NH2 and surface-inactive benzaldehyde. Both of them desorb from oil-water interface, resulting in a rapid oil-water separation of the Pickering emulsions. Alternating stabilization and phase separation of the Pickering emulsions over 3 cycles were demonstrated by adjusting the pH. The pH-switchable Pickering emulsions show great potential in application to effective oil-water separation of emulsions.

pH Switchable Emulsions Based on Dynamic Covalent Surfactants.

Dynamic covalent surfactants were designed to prepare pH switchable emulsions. A dynamic covalent bond between nonamphiphilic building blocks (polyethylenimine (PEI) and benzaldehyde (B)) was introduced to form the dynamic covalent surfactant PEI-B. The dynamic nature of covalent bond in PEI-B was confirmed by 1H NMR and fluorescence probe analysis. Stable emulsions were successfully prepared with interfacial active PEI-B at pH 7.8 with various water/paraffin oil ratios under sonication. When lowering the pH to 3.5, a complete phase separation was observed as a result of breaking dynamic covalent bond in the interfacial active PEI-B. After tuning the pH back to 7.8, stable emulsion was obtained again due to the reformation of the dynamic covalent bond and hence interfacial active PEI-B. The emulsification and demulsification were dependent on the formation and breaking of dynamic covalent bond in PEI-B. Such pH-triggered emulsification and demulsification can be switched at least three times. Application of dynamic covalent surfactants will open up a novel route for preparing responsive emulsions.

pH and Magnetism Dual-Responsive Pickering Emulsion Stabilized by Dynamic Covalent Fe3O4 Nanoparticles.

Herein, we describe pH and magnetism dual-responsive liquid paraffin-in-water Pickering emulsion stabilized by dynamic covalent Fe3O4 (DC-Fe3O4) nanoparticles. On one hand, the Pickerinfigureg emulsions are sensitive to pH variations, and efficient demulsification can be achieved by regulating the pH between 10 and 2 within 30 min. The dynamic imine bond in DC-Fe3O4 can be reversibly formed and decomposed, resulting in a pH-controlled amphiphilicity. The Pickering emulsion can be reversibly switched between stable and unstable states by pH at least three times. On the other hand, the magnetic Fe3O4 core of DC-Fe3O4 allowed rapid separation of the oil droplets from Pickering emulsions under an external magnetic field within 40 s, which was a good extraction system for purifying the aqueous solution contaminated by rhodamine B. The dual responsiveness enables Pickering emulsions to have better control of their stability and to be applied more broadly.

pH-Responsive Nanoemulsions Based on a Dynamic Covalent Surfactant.

Developing solid-free nanoemulsions with pH responsiveness is desirable in enhanced oil recovery (EOR) applications. Here, we report the synthesis of an interfacial activity controllable surfactant (T-DBA) through dynamic imine bonding between taurine (T) and p-decyloxybenzaldehyde (DBA). Instead of macroemulsions, nanoemulsions can be prepared by using T-DBA as an emulsifier. The dynamic imine bond of T-DBA enables switching between the active and inactive states in response to pH. This switching of interfacial activity was used to gate the stability of nanoemulsions, thus enabling us to turn the nanoemulsions off and on. Using such dynamic imine bonds to govern nanoemulsion stability could enable intelligent control of many processes such as heavy oil recovery and interfacial reactions.

Hot-melt Adhesive Bonding of Polyurethane/Fluorinated Polyurethane/Alkylsilane-Functionalized Graphene Nanofibrous Fabrics with Enhanced Waterproofness, Breathability, and Mechanical Properties.

Waterproof-breathable (WB) materials with outstanding waterproofness, breathability, and mechanical performance are critical in diverse consumer applications. Electrospun nanofibrous membranes with thin fiber diameters, small pore sizes, and high porosity have attracted significant attention in the WB fabric field. Hot-press treatment technology can induce the formation of inter-fiber fusion structures and hence improve the waterproofness and mechanical performance. By combining electrospinning and hot-press treatment technology, polyurethane/fluorinated polyurethane/thermoplastic polyurethane/alkylsilane-functionalized graphene (PU/FPU/TPU/FG) nanofiber WB fabric was fabricated. Subsequently, the morphologies, porous structure, hydrostatic pressure, water vapor transmission rate (WVTR), and stress-strain behavior of the nanofiber WB fabric were systematically investigated. The introduction of the hydrophobic FG sheet structure and the formation of the inter-fiber fusion structure greatly improved not only the waterproofness but also the mechanical performance of the nanofiber WB fabric. The optimized PU/FPU/TPU-50/FG-1.5 WB fabric exhibited an excellent comprehensive performance: a high hydrostatic pressure of 80.4 kPa, a modest WVTR of 7.6 kg m-2 d-1, and a robust tensile stress of 127.59 MPa, which could be used to achieve various applications. This work not only highlights the preparation of materials, but also provides a high-performance nanofiber WB fabric with huge potential application prospects in various fields.

CO2-responsive aqueous foams stabilized by pseudogemini surfactants.

HYPOTHESIS: To obtain surfactants with superior surface activity and responsive behavior, "pseudogemini" surfactants (short for D-LCFA) are synthesized by mixing long chain fatty acids (LCFA) and polyetheramine D 230 at fixed molar ratio (2:1). Non-covalently bonded building blocks indicate that CO2-responsive aqueous foams can be obtained by utilizing such pseudogemini surfactants. EXPERIMENTS: 1H NMR and FT-IR characterizations prove that the building blocks of these surfactants are associated by electrostatic interaction. The synthesis (Brønsted acid-base reaction) is simple and eco-friendly. "Pseudogemini" structure enables D-LCFA to reduce surface tension of aqueous solution effectively, thus facilitating foam generation. Rheograms, FF-TEM and Cryo-TEM results prove that different aggregates in D-LCFA aqueous solutions lead to different foam properties. FINDINGS: Bubbling of CO2 for about 30 s leads to the rupture of aqueous foams generated by D-LCFA, while removing CO2 by bubbling of N2 at 65 °C for 10 min enables re-generation of foams. The CO2-responsive foaming properties can be attributed to dissociation of D-LCFA upon bubbling of CO2 and re-association upon removal of CO2. The effective CO2-responsive foams can be applied to many areas, such as foam fracturing, foam enhanced oil recovery or recovering of radioactive materials.

Nanoemulsion formation by the phase inversion temperature method using polyoxypropylene surfactants.

HYPOTHESIS: Surfactants with temperature-sensitive polyoxyethylene (POE) chains are widely used to prepare nanoemulsions by the phase inversion temperature (PIT) method. It is therefore anticipated that surfactants with temperature-sensitive polyoxypropylene (POP) chains could also be used to prepare nanoemulsions by the PIT method. EXPERIMENT: POP surfactants were synthesized through electrostatic interactions between hydrophilic POP diamines and hydrophobic long-chain fatty acids. The synthesized POP surfactants were used as emulsifiers to prepare n-tetradecane-in-water nanoemulsions by the PIT method. Electrical conductivity measurements were used to determine the PITs of the water/POP surfactant/n-tetradecane systems. The effects of surfactant concentration, NaCl concentration, number of POP units, and degree of unsaturation of hydrocarbon chains on the PIT and the nanoemulsion droplet size were investigated. The droplet size and morphology of the nanoemulsions were characterized by dynamic light scattering and cryogenic transmission electron microscopy, respectively. FINDINGS: Nanoemulsions are formed by the PIT method using POP surfactants when the POP chains are short (∼2.5-6.1 POP units). The formation of nanoemulsions with droplet radii of 20-300 nm and spherical morphology occurs because of the temperature-dependent hydration of the short POP chains.

A fatty acid solvent of switchable miscibility.

Ion pair interactions were explored to design a fatty acid solvent of switchable miscibility with water. Fatty acids of medium length chains are immiscible with water but become miscible with water when ion pairs are formed with amines. The ion pairs become phase separated after bubbling CO2 into the solution due to the dissociation of the fatty acid-amine complexes. Ion pairs of caprylic acid (C8) and low toxic poly(oxypropylene) diamine (Jeffamine D-230) were characterized by FT-IR and 1H NMR. Log Kow values and surface activity were used to understand the switchable solvent mechanism in removing and recovering oily contaminants. More importantly, the ion pairs show a negligible adsorption on solid surfaces. Furthermore, both C8 and D-230 were recycled during the washing process. Thus the fatty acid as switchable solvent could be applied for oily contaminant removal from oily solid wastes.