Multicompartment polymer nanostructures with ratiometric dual-emission pH-sensitivity.

Pyrazine-labeled multicompartment nanostructures are shown to exhibit enhanced pH-responsive blue-shifted fluorescence emission intensities compared to their simpler core-shell spherical analogs. An amphiphilic linear triblock terpolymer of ethylene oxide, N-acryloxysuccinimide, and styrene, PEO(45)-b-PNAS(105)-b-PS(45), which lacks significant incompatibility for the hydrophobic block segments and undergoes gradual hydrolysis of the NAS units, underwent supramolecular assembly in mixtures of organic solvent and water to afford multicompartment micelles (MCMs) with a narrow size distribution. The assembly process was followed over time and found to evolve from individual polymer nanodroplets containing internally phase segregated domains, of increasing definition, and ultimately to dissociate into discrete micelles. Upon covalent cross-linking of the MCMs with pH-insensitive pyrazine-based diamino cross-linkers, pH-responsive, photonic multicompartment nanostructures (MCNs) were produced. These MCNs exhibited significant enhancement of overall structural stability, in comparison with the MCMs, and internal structural tunability through the cross-linking chemistry. Meanwhile, the complex compartmentalized morphology exerted unique pH-responsive fluorescence dual-emission properties, indicating promise in ratiometric pH-sensing applications.

Tunable dual-emitting shell-crosslinked nano-objects as single-component ratiometric pH-sensing materials.

Dual-emitting photonic nano-objects that can sense changes in the environmental pH are designed based on shell-crosslinked micelles assembled from amphiphilic block copolymers and crosslinked with pH-insensitive chromophores. The chromophoric crosslinkers are tetra-functionalized pyrazine molecules that bear a set of terminal aliphatic amine groups and a set of anilino amine groups, which demonstrate morphology-dependent reactivities towards the poly(acrylic acid) shell domain of the nano-objects. The extent to which the anilino amine groups react with the nano-object shell is shown to affect the hypsochromic shift (blue-shift). The ratio of fluorescence intensity at 496 nm over that of 560 nm is dependent upon the solution pH. We report, herein, observations on the pH-sensitive dual-emission photophysical properties of rod-shaped or spherical nano-objects, whose shell domains offer two distinct platforms for amidation reactions to occur-through formation of activated esters upon addition of carbodiimide or pre-installation of activated ester groups. We demonstrate that physical manipulations (changes in morphology or particle dimensions) or chemical manipulations of the crosslinking reaction (the order of installation of activated esters) lead to fine tuning of dual-emission over ca. 60 nm in a physiologically relevant pH range. Rod-shaped shell-crosslinked nanostructures with poly(p-hydroxystyrene) core show blue-shift as a function of increasing pH while spherical shell-crosslinked nanostructures with polystyrene core and poly(ethylene oxide) corona exhibit blue-shift as a function of decreasing pH.

Photonic Shell-Crosslinked Nanoparticle Probes for Optical Imaging and Monitoring.

A pH-insensitive fluorophore is made to give pH-driven responses through its covalent incorporation within a nanostructure derived from pH-responsive polymers. Fluorophore-shell-crosslinked nanoparticles (SCKs) demonstrate notable enhancement of photophysical properties, in the physiological pH region. Fluorophore-SCKs are designed to swell at higher pH and shrink as the pH is lowered, producing high fluorescence vs. low fluorescence outputs, respectively.