Nanoparticle Surfactants at Complex Emulsion Interfaces.

Using nanoparticle surfactants to stabilize the liquid-liquid interface has attracted significant attention for developing all-liquid constructs including emulsions and liquid devices. Here, an efficient strategy is demonstrated to stabilize complex emulsions that consist of multiphase droplets by using the co-assembly between the cellulose nanocrystal and amine-functionalized polystyrene. Cellulose nanocrystal surfactants (CNCSs) form and assembly in situ at the specified area of emulsion interface, showing a unique pH responsiveness due to their dynamic nature and allowing the reconfiguration of complex emulsion from encapsulated to Janus structures.

All-oil Constructs Stabilized by Cellulose Nanocrystal Surfactants.

Constructing all-oil systems with desired geometries and responsiveness would produce a new class of reconfigurable materials that can be used for applications that are not compatible with water or aqueous systems, a fascinating goal to achieve but severely limited by the lack of surfactants. Here, we demonstrate an efficient strategy to stabilize oil-oil interfaces by using the co-assembly between the cellulose nanocrystal and amine-functionalized polyhedral oligomeric silsesquioxane (POSS-NH). Cellulose nanocrystal surfactants (CNCSs) form and assemble in situ at the interface, showing significantly enhanced binding energy and acid-dependent interfacial activity.

Supramolecular Interfaces and Reconfigurable Liquids Derived from Cucurbit[7]uril Surfactants.

Nanoparticle surfactants (NPSs) offer a powerful means to stabilize the oil-water interface and construct all-liquid devices with advanced functions. However, as the nanoparticle size decreases to molecular-scale, the binding energy of the NPS to the interface reduces significantly, leading to a dynamic adsorption of NPS and "liquid-like" state of the interfacial assemblies. Here, by using the host-guest recognition between a water-soluble small molecule, cucurbit[7]uril (CB[7]) and an oil-soluble polymer ligand, methyl viologen-terminated polystyrene, a supramolecular NPS model, termed CB[7] surfactant, is described.

Reconfigurable Liquids Constructed by Pillar[6]arene-Based Nanoparticle Surfactants.

The interfacial jamming of nanoparticle surfactants offers the possibility of structuring liquids and fabricating all-liquid constructs with advanced functionality. However, less attention has been given to structured liquids with multiple responsiveness. Here, we show a novel, yet highly simplified nanoparticle surfactant model, pillar[6]arene (PA[6]) surfactant, by taking advantage of the host-guest interactions between a water-soluble PA[6] and an oil-soluble ligand, ferrocenium terminated polystyrene.

Redox-Responsive, Reconfigurable All-Liquid Constructs.

Using host-guest chemistries in a biphasic system, a novel supramolecular nanoparticle surfactant (s-NPS) with redox-responsiveness is presented to structure liquids. The in situ assembly/jamming and disassembly/unjamming of s-NPSs at the oil-water interface are reversibly controlled by a switchable redox process, imparting a nanoscale redox-responsiveness, affecting the assemblies on all length scales. "Smart" all-liquid constructs including structured emulsions and programmable liquid devices are easily prepared, showing promising applications in responsive delivery, release, and reaction systems.

Chiral Phosphoric Acid Catalyzed Enantioselective Synthesis of α-Tertiary Amino Ketones from Sulfonium Ylides.

Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones, which is particularly useful for the less accessible acyclic α-tertiary cases. By a protonation-amination sequence, our approach represents a rare asymmetric H-heteroatom bond insertion by α-carbonyl sulfonium ylides, an attractive surrogate of diazocarbonyls. The mild intermolecular C-N bond formation was catalyzed by chiral phosphoric acids with excellent efficiency and enantioselectivity.

Short-term outcomes of rapid initiation of antiretroviral therapy among HIV-positive patients: real-world experience from a single-centre retrospective cohort in Taiwan.

Objectives: Rapid initiation of antiretroviral therapy (ART) engenders faster viral suppression but with suboptimal rates of durable viral suppression and engagement in care, as reported by clinical trials in resource-limited settings. Real-world experience with rapid ART initiation remains limited in resource-rich settings.

Design: Retrospective cohort study.

Synthesis of α-heterosubstituted ketones through sulfur mediated difunctionalization of internal alkynes.

Synthesis of α-heterosubstituted ketones was achieved through sulfur mediated difunctionalization of internal alkynes in one pot. The reaction design involves: phenyl substituted internal alkyne attacking triflic anhydride activated diphenyl sulfoxide to give a sulfonium vinyl triflate intermediate, hydrolysis to give an α-sulfonium ketone, and then substitution with various nucleophiles. This method provides a unified route to access α-amino ketones, α-acyloxy ketones, α-thio ketones, α-halo ketones, α-hydroxy ketones, and related heterocyclic structures, in a rapid fashion.