Substantial Confinement of Crystal Growth of Organic Crystalline Materials in Metal-Organic Membrane Microshells.

This study proposes a robust microshell encapsulation system in which a metal-organic membrane (MOM), consisting of phytic acids (PAs) and metal ions, intrinsically prevents the molecular crystal growth of organic crystalline materials (OCMs). To develop this system, OCM-containing oil-in-water (O/W) Pickering emulsions were enveloped with the MOM, in which anionic pulp cellulose nanofiber (PCNF) primers electrostatically captured zinc ions at the O/W interface and chelated with PA, thus producing the MOM with a controlled shell thickness at the micron scale. We ascertained that the MOM formation fills and covers ∼75% of the surface pore size of PCNF films, which enhances the interfacial modulus by 2 orders of magnitude compared to that when treated with bare PCNFs. Through a feasibility test using a series of common OCMs, including ethylhexyl triazone, avobenzone, and ceramide, we demonstrated the excellent ability of our MOM microshell system to stably encapsulate OCMs while retaining their original molecular structures over time. These findings indicate that our MOM-reinforced microshell technology can be applied as a platform to substantially confine the crystal growth of various types of OCMs.

Shear-Responsive Sol-Gel Transition of Phase Change Material Emulsions for an Injectable Thermal Insulation Platform.

Phase change materials (PCMs) have attracted significant attention as promising insulating materials. However, they often suffer from the simple yet critical problem of leakage in practical applications. Therefore, in this study, an injectable PCM emulsion insulation platform is developed. For this, n-hexadecane, as a PCM, emulsion droplets are armored with a metal-organic membrane (MOM) through the coordination of zinc ions and phytic acid. The MOM layer not only provides a rigid interfacial modulus but also allows the emulsion to exhibit viscoelastic behavior by shear stress-induced interdrop association. This MOM-enveloped PCM emulsion (PCMEMOM ) exhibited typical sol-gel transition behavior in response to applied shear stress, indicating the injectable characteristic of the PCMEMOM . After observing the rheological hysteresis and thermal stability of the PCMEMOM under repetitive heating and cooling cycles, the thermal insulation performance of PCMEMOM is quantitatively and visually demonstrated. These findings suggest an efficient method to exploit high-performance insulation systems.

High Internal Phase Emulsion Stabilization through Restricted Interdrop Fusion across Water Drainage Channels.

This study introduces a promising approach to stabilize high internal phase emulsions (HIPEs) in which droplets are enveloped by octadecane (C18)-grafted bacterial cellulose nanofibers (BCNFdiC18), which are mainly surrounded by carboxylate anions and hydrophobically modified with C18 alkyl chains. For this purpose, BCNFdiC18, in which two octadecyl chains were grafted onto each of several cellulose unit rings on 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidized BCNFs, was fabricated using the Schiff base reaction. The wettability of BCNFdiC18 was adjusted by controlling the amount of the grafted C18 alkyl chain. Interfacial rheological analysis revealed that BCNFdiC18 enhanced the membrane modulus at the oil-water interface. We figured out that such a resilient interfacial membrane substantially prevented interdrop fusion across the water drainage channel formed between the jammed oil droplets, which was confirmed theoretically using the modified Stefan-Reynolds equation. These findings highlight that the use of surfactants in the form of nanofibers to form a rigid interfacial film plays a key role in hindering the interfusion of the internal phase and the collapse of the emulsion, which is essential for HIPE stabilization.

Two-dimensional demixing within multilayered nanoemulsion films.

Benefiting from the demixing of substances in the two-phase region, a smart polymer laminate film system that exhibits direction-controlled phase separation behavior was developed in this study. Here, nanoemulsion films (NEFs) in which liquid nanodrops were uniformly confined in a polymer laminate film through the layer-by-layer deposition of oppositely charged emulsion nanodrops and polyelectrolytes were fabricated. Upon reaching a critical temperature, the NEFs exhibited a micropore-guided demixing phenomenon. A simulation study based on coarse-grained molecular dynamics revealed that the perpendicular diffusion of oil droplets through the micropores generated in the polyelectrolyte layer is crucial for determining the coarsening kinetics and phase separation level, which is consistent with the experimental results. Considering the substantial advantages of this unique and tunable two-dimensional demixing behavior, the viability of using the as-proposed NEF system for providing an efficient route for the development of smart drug delivery patches was demonstrated.