Visual demonstration and prediction of the Hofmeister series based on a poly(ionic liquid) photonic array.

The Hofmeister effect and associated Hofmeister series (HS) are ubiquitous in physicochemical phenomena and have demonstrated fundamental importance in a myriad of fields ranging from chemistry to biology. Visualization of the HS not only helps to straightforwardly understand the underpinning mechanism, but also enables the prediction of new ion positions in the HS and directs the applications of the Hofmeister effect. Owing to the difficulties of sensing and reporting complete multiple and subtle inter- and intramolecular interactions involved in the Hofmeister effect, facile and accurate visual demonstration and prediction of the HS remain highly challenging. Herein, a poly(ionic liquid) (PIL)-based photonic array containing 6 inverse opal microspheres was rationally constructed to efficiently sense and report the ion effects of the HS. The PILs can not only directly conjugate with HS ions due to their ion-exchange properties, but also provide sufficient noncovalent binding diversity with these ions. Meanwhile, subtle PIL-ion interactions can be sensitively amplified to optical signals owing to their photonic structures. Therefore, synergistic integration of PILs and photonic structures gives rise to accurate visualization of the ion effect of the HS, as demonstrated by correctly ranking 7 common anions. More importantly, assisted by principal component analysis (PCA), the developed PIL photonic array can serve as a general platform to facilely, accurately, and robustly predict the HS positions of an unprecedented amount of important and useful anions and cations. These findings indicate that the PIL photonic platform is very promising for addressing challenges in the visual demonstration and prediction of HS and promoting a molecular-level understanding of the Hoffmeister effect.

AIE-doped Poly(Ionic Liquid) Photonic Spheres for the Discrimination of Psychoactive Substances.

Drugs of abuse has drawn intense attention due to increasing concerns to public health and safety. The construction of a sensing platform with the capability to identify them remains a big challenge because of the limitations of synthetic complexity, sensing scope and receptor extendibility. Here a kind of poly(ionic liquid) (PIL) photonic crystal spheres doped with aggregation-induced emission (AIE) luminogens was developed. As diverse noncovalent interactions involve in PIL moieties, the single sphere shows different binding affinity to a broad range of psychoactive substances. Furthermore, the dual-channel signals arising from photonic crystal structures and sensitive AIE-luminogens provide high-dimensional information for discriminative detection of targets, even for molecules with slight structural differences. More importantly, such single sphere sensing platform could be flexibly customized through ion-exchange, showing great extendibility to fabricate high-efficiency/high-throughput sensing arrays without tedious synthesis.

Arrested Coalescence of Ionic Liquid Droplets: A Facile Strategy for Spatially Organized Multicompartment Assemblies.

Multicompartment assemblies attract much attention for their wide applications. However, the fabrication of multicompartment assemblies usually requires elaborately designed building blocks and careful controlling. The emergence of droplet networks has provided a facile way to construct multiple droplet architectures, which can further be converted to multicompartment assemblies. Herein, the bind motif-free building blocks are presented, which consist of the hydrophobic Tf2 N- -based ionic liquid (IL) dissolving LiTf2 N salt, that can conjugate via arrested coalescence in confined-space templates to form IL droplet networks. Subsequent ultraviolent polymerization generates robust free-standing multicompartment assemblies. The conjugation of building blocks relies not on the peripheral bind motif but on the interfacial instability-induced arrested coalescence, avoiding tedious surface modification and assembly process. By tuning structures of templates and building blocks, multicompartment assemblies with 0D, 1D, 2D, and 3D structures are prepared in a facile and high-throughput way. Importantly, the bottom-up construction enables modular control over the compositions and spatial positions of individual building blocks. Combining with the excellent solvency of ILs, this system can serve as a general platform towards versatile multicompartment architectures. As demonstrations, by tailoring the chambers the multicompartment assemblies can spatiotemporally sense and report the chemical cues and perform various modes of motion.

Rational Approach to Plasmonic Dimers with Controlled Gap Distance, Symmetry, and Capability of Precisely Hosting Guest Molecules in Hotspot Regions.

Plasmonic dimers not only provide a unique platform for studying fundamental plasmonic behavior and effects but also are functional materials for numerous applications. The efficient creation of well-defined dimers with flexible control of structure parameters and thus tunable optical property is the prerequisite for fully exploiting the potential of this nanostructure. Herein, based on a polymer-assisted self-assembly approach in conjugation with molecular cage chemistry, a strategy was demonstrated for constructing cage-bridged plasmonic dimers with controlled sizes, compositions, shape, symmetry, and interparticle gap separation in a modular and high-yield manner. With a high degree of freedom and controllability, this strategy allows facilely accessing various symmetrical/asymmetrical dimers with sub-5 nm gap distance and tailored optical properties. Importantly, as the linkage of the two constituent elements, the molecular cages embedded in the junction endow the assembled dimers with the ability to precisely and reversibly host rich guest molecules in hotspot regions, offering great potential for creating various plasmon-mediated applications.

A Reductive Supramolecular Hydrogel: A Platform for Facile Fabrication of Diverse Metal-Nanoparticle-Decorated Conductive Networks with Spatiotemporal Control.

Nanoparticle-hydrogel hybrid composites have a great potential for a broad range of applications, such as antibacterial materials, stimuli-responsive materials and catalysis. A novel supramolecular hydrogel system was developed using an amino acid based amphiphile containing a terminal pyrrole moiety as a gelator. The pyrrole moiety could serve as both reducing agent and monomer, and a variety of metal precursors penetrating into the hydrogel could be reduced in situ into metal nanoparticles while the pyrrole moieties preorganized in hydrogel were oxidized into polyprroles, affording metal-nanoparticle-decorated covalent conductive networks. This strategy allows the facile fabrication of diverse mono- or multimetallic nanoparticle-polymer networks from one hydrogel by a simple reaction-diffusion approach. More importantly, besides homogeneous composites, unique multisegment heterogeneous systems with spatiotemporal control were also easily accessible. Furthermore, based on the same multifunctional molecule, the fabrication of hierarchically pore-structured metal-nanoparticles-polymers as well as metal-nanoparticles-carbon structures was also realized.

Creation of Nonspherical Microparticles through Osmosis-Driven Arrested Coalescence of Microfluidic Emulsions.

Droplet-based microfluidics enable the production of emulsions and microparticles with spherical shapes, but the high-throughput fabrication of nonspherical emulsions and microparticles still remains challenging because interfacial tension plays a dominant role during preparation. Herein, ionic liquids (ILs) containing salts, which possess sufficient osmotic pressure to realize water transport and phase separation, are introduced as inner cores of oil-in-oil-in-water double emulsions and it is shown that nonspherical emulsions can be constructed by osmosis-driven arrested coalescence of inner cores. Subsequently, ultraviolet polymerization of the nonspherical emulsions leads to nonspherical microparticles. By tailoring the number, composition, and size of inner cores as well as coalescence time, a variety of nonspherical shapes such as dumbbell, rod, spindle, snowman, tumbler, three-pointed star, triangle, and scalene triangle are created. Importantly, benefitting from excellent solvency of ILs, this system can serve as a general platform to produce nonspherical microparticles made from different materials. Moreover, by controlling the osmotic pressure, programmed coalescence of inner cores in double emulsions is realizable, which indicates the potential to build microreactors. Thus, a simple and high-throughput strategy to create nonspherical microparticles with arrested coalescence shapes is developed for the first time and can be further used to construct novel materials and microreactors.