How Does Chemistry Influence Liquid Wettability on Liquid-Infused Porous Surface?

Design of Nepenthes pitcher-inspired slippery liquid-infused porous surface (SLIPS) appeared as an important avenue for various potential and practically relevant applications. In general, hydrophobic base layers were infused with selected liquid lubricants for developing chemically inert SLIPS. Here, in this current study, an inherently hydrophilic (soaked beaded water droplet with ∼20° within a couple of minutes), porous and thick (above 200 µm) polymeric coating, loaded with readily chemically reactive acrylate moieties yielded a chemically reactive SLIPS, where residual acrylate groups in the synthesized hydrophilic and porous interface rendered stability to the infused lubricants. The chemically reactive SLIPS is capable of reacting with the solution of primary amine-containing nucleophiles in organic solvent through 1,4-conjugate addition reaction, both in the presence (referred as "in situ" modification) and absence (denoted as pre-modification) of lubricated phase in the porous polymeric coating. Such amine reactive SLIPS was further extended to (1) examining the impact of different chemical modifications on the performance of SLIPS and (2) developing a spatially selective and "in situ" postmodification with primary amine-containing nucleophiles through 1,4-conjugate addition reaction. Moreover, the chemically reactive SLIPS was capable of sustaining various physical abrasions and prolonged (minimum 10 days) exposure to complex and harsh aqueous phases, where infused lubricants protect the residual acrylate groups from harsh aqueous exposures. Such, principle will be certainly useful for spatially selective covalent immobilization of water-insoluble functional molecules/polymers directly from organic solvents, which would be of potential interest for various applied and fundamental contexts.

Facile optimization of hierarchical topography and chemistry on magnetically active graphene oxide nanosheets.

Highly flexible and two-dimensional (2D) graphene oxide (GO) nanosheets have remained instrumental for developing different functional materials for practically relevant applications. In general, 2D GO is routinely assembled into different structures (i.e. layered, porous, etc.) for achieving desired properties. However, a facile approach for modifying GO nanosheets with (1) hierarchical topography and (2) desired chemistry is rare in the literature. In this report, adequate optimization of both hierarchical topography and low surface energy chemistry in a confined space (in the order of µm dimensions) of GO nanosheets is unprecedentedly carried out for achieving magnetically active and 2D 'confined-super-water-repellence'. A chemically reactive polymeric complex was covalently deposited on the GO-nanosheets through a facile 1,4-conjugate addition reaction for adopting a chemically reactive and hierarchically featured polymeric interface. Simultaneously, the deposition of iron oxide nanoparticles on the 2D-nanosheets rendered the entire material magnetically active. The post-covalent modification of these chemically/magnetically active and hierarchically featured GO-nanosheets with octadecylamine (ODA) yielded magnetically active and 2D 'confined-superhydrophobicity'. Further, this synthesized material was extended for addressing highly relevant and severe global challenges of 'oil-in-water' and 'water-in-oil' emulsion separation by either selective collection (with an efficiency of above 1000 wt%) of tiny oil-droplets from bulk water or forming magnetically active 'Pickering-type' aqueous droplets, respectively, under various practically relevant harsh conditions, including extremes of pH, salinity, surfactant contamination, etc. Further, appropriate functionalization of this chemically/magnetically active 2D nano-interface could be useful in developing functional interfaces for various applications related to energy, catalysis and healthcare.

A Scalable Chemical Approach for the Synthesis of a Highly Tolerant and Efficient Oil Absorbent.

In the past, bio-inspired extreme water repellent property has been strategically embedded on commercially available sponges for developing selective oil absorbents. However, most of the reported materials lack physical and chemical durability, limiting their applicability at practically harsh settings. Herein, a stable dispersion of polymeric nanocomplexes was exploited to achieve a chemically reactive coating on the highly compressible melamine foam. A superhydrophobic melamine foam (SMF) was achieved after post-covalent modification of the reactive coating through 1,4-conjugate addition reaction at ambient conditions. The durability of the embedded extreme water repellent property in the as-modified melamine foam has been elaborately demonstrated through exposing it to severe physical manipulations, chemically harsh aqueous media including pH 1, pH 12, surfactant contaminated water, river water, seawater and prolonged UV irradiation. Thus, the highly tolerant SMF was utilized as an efficient oil absorbent wherein oils of varying densities could be selectively recovered from an oil/water interface with high (e.g., 137 g g-1 for chloroform and 83 g g-1 for diesel) oil absorption capacity. Moreover, the selective oil absorption capacity of the as-synthesized material remained unaffected at practically relevant severe chemical and physical settings, and the extreme water repellency of the material remained unaltered even after repetitive (at least 50 cycles) use for oil/water separation.

'Reactive' nano-complex coated medical cotton: a facile avenue for tailored release of small molecules.

Controlled and sustained release of drug-like small molecules in an aqueous medium still remains a challenging problem due to rapid infiltration of liquid water in most reported drug release systems. However, internal-superhydrophobicity with an antifouling property extending beyond the surface of a material recently has been recognized as a potential avenue for sustained and extended release of drug-like small molecules. Sluggish removal of metastable trapped air in a superhyrophobic material provides a basis to achieve extended release of encapsulated small molecules. In this article, naturally abundant medical-cotton-extensively used in wound management including control of bleeding, absorbance of secretions and protecting wounds from contamination-is strategically exploited in tailoring (from rapid to extended) the release of small molecules by appropriate modulation of liquid water wettability. Modulation included bio-mimicked adhesive and non-adhesive superhydrophobicity of the medical cotton without erosion of any polymeric material. In this process, amine 'reactive' nano-complexes (RNC) were prepared by just mixing branched poly(ethylenimine) (BPEI) with dipentaerythritol pentaacrylate (5Acl) in ethanol with appropriate compositions. Then they were covalently immobilized on fibrous medical-cotton through a facile and robust 1,4-conjugated addition reaction. Residual acrylate moieties in the immobilized RNC provide an opportunity to tailor water wettability through strategic and appropriate post-chemical modification of RNC-coated medical cotton with a primary amine containing various small molecules. This medical-cotton with tunable wettability was exploited further to control the release rate of small molecules from rapid (<24 h) to sustained (>100 days) times. A volatile solvent induced transient and reversible switching of anti-fouling properties which allowed further varying the amount of post-loading small molecules into the medical cotton up to 2.36 wt% without compromising the embedded anti-wetting property. Thus, our current approach has immense potential to develop appropriate materials for a sustained and controlled release of small molecules from a clinically relevant substrate (i.e., medical-cotton) and may be useful in various bio-medical applications including improving wound management, preventing bacterial infections, better pain management, etc.