Mesoporous, anisotropic nanostructures from bioinspired polymeric catecholamine neurotransmitters and their potential application as photoacoustic imaging agents

Mesoporous polydopamine (PDA) nanobowls, which can be prepared using Pluronic® F-127, ammonia, and 1,3,5-trimethylbenzene (TMB), are one of the most studied anisotropic nanoparticle systems. However, only limited reports on polymerised analogues polynorepinephrine (PNE) and polyepinephrine (PEP) exist. Herein, we present modifications to a one-pot, soft template method, originally applied to make PDA nanobowls, to fabricate new shape-anisotropic nanoparticles (mesoporous nanospheres or "nano-golf balls" and nanobowls) using PNE and PEP for the first time. These modifications include the use of different oil phases (TMB, toluene and o-xylene) and ammonia concentrations to induce anisotropic growth of PDA, PNE, and PEP particles. Moreover, this work features the application of oddly shaped PDA, PNE, and PEP nanoparticles as intravascular photoacoustic imaging enhancers in Intralipid®-India ink-based tissue-mimicking phantoms. Photoacoustic imaging experiments showed that mesoporous nanobowls exhibit stronger enhancement, in comparison to their mesoporous nano-golf ball and nanoaggregate counterparts. The photoacoustic enhancement also followed the general trend PDA > PNE > PEP due to the differences in the rates of polymerisation of the monomers and the optical absorption of the resulting polymers. Lastly, about two- to four-fold enhancement in photoacoustic signals was observed for the mesoporous nanostructures, when compared to smooth nanospheres and their nano-aggregates. These results suggest that shape manipulation can aid in overcoming the inherently lower performance of PNE and PEP as photoacoustic imaging agents, compared to PDA. Since nanomaterials with mesoporous and anisotropic morphologies have significant, unexplored potential with emerging applications, these results set the groundwork for future studies on photoacoustically active oddly shaped PNE- and PEP-based nanosystems.