Self-regulatory Enzyme-actuated Macroscale Patterning of ATP-loaded Nanoparticle

Directional interactions and assembly of nanobioconjugate in clusters at specific location are important for patterning, microarrays to biomedical research. Herein, we report self-assembly and spatial control in surface patterning of the surfactant-functionalized nanoparticles can be governed in macroscale environment by two factors – synergistic enzyme-substrate-nanoparticle affinity and phoretic effect. Firstly, we showed aggregation of cationic gold nanoparticle (GNP) can be modulated by multivalent anionic nanoparticle binding adenosine-based nucleotide and enzyme, alkaline phosphatase. We further demonstrated two different types of their autonomous aggregation pattern – (i) by introducing enzyme gradient which modulates the synergistic non-equilibrium interactivity of the nanoparticle, nucleotide and enzyme in macroscale and (ii) surface deposition pattern from evaporating droplet via coffee ring effect. Finally, we showed change in capillary phoresis parameters responsible for coffee ring due to introduction of ATP-loaded GNP in blood serum, showing immense applicability in low-cost disease diagnostics. Overall, a unique method for macroscale surface nanobiopatterning has been demonstrated having potential application in controlled large area patterning with diverse cascade catalytic surface and spatiotemporal multisensory-based application.