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.

Ultralight, Robust, Thermal Insulating Silica Nanolace Aerogels Derived from Pickering Emulsion Templates.

Synthesis of silica aerogel insulators with ultralight weight and strong mechanical properties using a simplified technique remains challenging for functional soft materials. This study introduces a promising method for the fabrication of mechanically reinforced ultralight silica aerogels by employing attractive silica nanolace (ASNLs)-armored Pickering emulsion templates. For this, silica nanolaces (SiNLs) are fabricated by surrounding a cellulose nanofiber with necklace-shaped silica nanospheres. In order to achieve amphiphilicity, which is crucial for the stabilization of oil-in-water Pickering emulsions, hydrophobic alkyl chains and hydrophilic amine groups are grafted onto the surface of SiNLs by silica coupling reactions. Freeze-drying of ASNLs-armored Pickering emulsions has established a new type of aerogel system. The ASNLs-supported mesoporous aerogel shows 3-fold greater compressive strength, 4-fold reduced heat transfer, and a swift heat dissipation profile compared to that of the bare ASNL aerogel. Additionally, the ASNL aerogel achieves an ultralow density of 8 mg cm-3, attributed to the pore architecture generated from closely jammed emulsion drops. These results show the potential of the ASNL aerogel system, which is ultralight, mechanically stable, and thermally insulating and could be used in building services, energy-saving technologies, and the aerospace industry.

Microphase transitions of Langmuir-Blodgett lipid-assembled monolayers with new types of ceramides, ultra-long-chain ceramide and 1-O-acylceramide.

HYPOTHESIS: Intercellular lipid lamellae, consisting of ceramide, cholesterol, and free fatty acids, are the primary pathways for substances in the stratum corneum (SC). The microphase transition of lipid-assembled monolayers (LAMs), mimicking an initial layer of the SC, would be affected by new types of ceramides: ceramide with ultra-long chain (CULC) and 1-O-acylceramide (CENP) with three chains in different direction. EXPERIMENTS: The LAMs were fabricated with varying the mixing ratio of CULC (or CENP) against base ceramide via Langmuir-Blodgett assembly. Surface pressure-area isotherms and elastic modulus-surface pressure plots were obtained to characterize π-dependent microphase transitions. The surface morphology of LAMs was observed by atomic force microscopy. FINDINGS: The CULCs favored lateral lipid packing, and the CENPs hindered the lateral lipid packing by lying alignment, which was due to their different molecular structures and conformations. The sporadic clusters and empty spaces in the LAMs with CULC were presumably due to the short-range interactions and self-entanglements of ultra-long alkyl chains following the freely jointed chain model, respectively, which was not noticeably observed in the neat LAM films and the LAM films with CENP. The addition of surfactants disrupted the lateral packing of lipids, thus weakening the LAM elasticity. These findings allowed us to understand the role of CULC and CENP in the lipid assemblies and microphase transition behaviors in an initial layer of SC.

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.

Energetically Preferred Bilayered Coacervation of Oppositely Charged ZrHP Nanoplatelets.

A platform is introduced for bilayered coacervation of oppositely charged nanoplatelets (NPLs) at the oil-water interface. To this end, we synthesized two types of zirconium hydrogen phosphate (ZrHP) NPLs, cationically charged NPLs (CNPLs), and anionically charged NPLs (ANPLs) by conducting surface-initiated atom transfer radical polymerization. Taking advantage of the platelet geometry and controlled wettability, we demonstrated that ANPLs and CNPLs coacervate themselves to form a bilayered NPL membrane at the interface, which was directly confirmed by confocal laser scanning microscopy. Via theoretical consideration using the hit-and-miss Monte Carlo method, we determined that electrostatic attraction-driven coacervation of ANPLs and CNPLs at the interface shows a minimum attachment energy of ∼ -106 kBT, which is comparable to the cases where NPLs charged with the same type of ions are attached. Finally, this unique and novel interfacial coacervation behavior allowed us to develop a pH-responsive smart Pickering emulsion system.

Janus amphiphilic nanoplatelets as smart colloid surfactants with complementary face-to-face interactions.

We introduce amphiphilic nanoplatelets (ANPLs) that not only have a nanoscale Janus platelet geometry, but can also induce complementary face-to-face interactions among Pickering emulsion droplets. We showed that the ANPLs with such high surface activity can be a promising colloid surfactant enabling smart rheology modification of complex emulsion fluids.

Effective association of ceramide-coassembled lipid nanovehicles with stratum corneum for improved skin barrier function and enhanced skin penetration.

Herein, we report on a ceramide-coassembled lipid nanovehicle (CLNV) system that can enhance the penetration of active ingredients through the skin barrier by taking advantage of molecular associations between ceramide and lipids in the stratum corneum (SC) layer. For this purpose, we fabricated CLNVs consisting of an asymmetric lipid and a cholesterol derivative. They showed excellent long-term dispersion stability without molecular crystallization of ceramide. Upon forming a stable aqueous dispersion, the CLNVs retained their initial vehicle structure even under harsh conditions including high storage temperatures or salinity conditions. From in vitro skin barrier recovery tests, we observed that topical treatment with CLNVs induced the SC to restore its lamellar structure to the same condition as that prior to chemical damage. An in vivo skin penetration study additionally confirmed that skin penetration was enhanced, since the CLNVs were able to effectively interact with the SC layer. From these results, the CLNVs with robust molecular layer endow various applications in wide range applications including transdermal pharmaceutics delivery systems and cosmetics field.