Entropically and enthalpically driven self-assembly of a naphthalimide-based luminescent organic π-amphiphile in water.

The self-assembly of π conjugated systems in water has emerged as an efficient method for the development of functional materials for biological applications. But the process is more difficult to understand and to control in water compared to organic solvents due to hydrophobic effects. For π-conjugated molecules, self-assembly in solution generally occurs due to either an enthalpic or entropic gain, but designing π systems that undergo self-assembly both an entropically and enthalpically favorable process is challenging.

Small molecule-based core and shell cross-linked nanoassemblies: from self-assembly and programmed disassembly to biological applications.

Supramolecular assemblies of stimuli-responsive amphiphilic molecules have been of utmost interest in targeted drug delivery applications, owing to their capability of sequestering drug molecules in one set of conditions and releasing them in another. To minimize undesired disassembly and stabilize noncovalently encapsulated drug molecules, the strategy of core or shell cross-linking has become a fascinating approach to constructing cross-linked polymeric or small molecule-based nanoassemblies. In this article, we discuss the design and synthetic strategies for cross-linked nanoassemblies from small molecule-based amphiphiles, with robust stability and enhanced drug encapsulation capability.

Anion-assisted supramolecular polymerization of luminescent organic π-conjugated chromophores in a moderately polar solvent: tunable nanostructures and their corresponding effects on electronic properties.

Supramolecular polymers of π-conjugated organic chromophores have emerged as promising candidates in organic electronics because of their dynamic and highly ordered molecular organization. Herein, we demonstrate the formation of luminescent, highly conducting supramolecular polymers of a functionalized naphthalimide π-chromophore-based organic semiconductor in a moderately polar organic solvent (tetrahydrofuran) by overcoming solute-solvent H-bonding assistance from fluoride anions. The polymerization is exclusively guided by the synergistic effects of cascade H-bonding (F⋯H-N- of primary amines, followed by -CO⋯H-N- of amides), π-π stacking and hydrophobic interactions.

Tumor acidity-induced surface charge modulation in covalent nanonetworks for activated cellular uptake: targeted delivery of anticancer drugs and selective cancer cell death.

A β-thioester and tertiary amine based covalently cross-linked nanoassembly coined as a nanonetwork (NN) endowed with dual pH responsive features (tumor acidity induced surface charge modulation and endosomal pH triggered controlled degradation) has been designed and synthesized for stable sequestration and sustained release of drug molecules in response to endosomal pH. An amphiphile integrated with tertiary amine and acrylate (ATA) functionalities was synthesized to fabricate the nanonetwork. This amphiphile showed entropically driven self-assembly and micellar nanostructures (nanoassemblies), which can sequester hydrophobic drug molecules at neutral pH.

Programmed supramolecular nanoassemblies: enhanced serum stability and cell specific triggered release of anti-cancer drugs.

A bolaamphiphilic cross-linked nanoassembly endowed with pH responsive degradation features has been designed and fabricated for stable noncovalent guest encapsulation and controlled release. The self-assembled bolaamphiphile is utilized to prepare cross-linked nanoassemblies to further stabilize the noncovalent guest encapsulation at a concentration below its critical aggregation concentration (CAC) in a large volume of water or serum for drug delivery applications. Thus, this system can simultaneously address premature drug release and safety issues.