Design of robust interface having an efficient water harvesting ability is important for more realistic application. Here, a dual chemically reactive porous polymeric interface is introduced to adopt various bio-inspired...
Three-dimensional, controlled and covalent chemical optimization is introduced through strategic exploitation of a facile 1,4-conjugate addition reaction and a scalable spray deposition process for synthesizing durable biomimicked interfaces.
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.
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.
‘Confined-optimization’ of desired topography and appropriate chemistry on a magnetically-active and two-dimensional (2D) graphene oxide (GO) nanosheets is unprecedentedly achieved following a rapid and facile 1,4-conjugate addition reaction.
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