Incorporating adaptive and dynamic behavior in a catalytic system is the foremost prerequisite to gain nature-like complex functionality in a synthetic chemical network. Herein, we report a self-assembled modular catalytic system based on the multivalent interaction between a cationic gold nanoparticle surface and nucleotides. It is shown that the catalytic preference and activity of the nanoparticle can be directed in a controllable manner toward either hydrazone formation or a proton transfer reaction only by creating a differential local microenvironment around the nanoparticle surface, simply by changing or converting the multivalent scaffold around it. The temporal control of the system in governing the reaction preference and catalytic activity will enable designing a system of higher complexity with a preprogrammed reaction networking property.

Predicting and designing system with dynamic self-assembling property in spatiotemporal fashion is an important research area across disciplines ranging from understanding fundamental non-equilibrium features of life to fabrication of next-generation...

Attainment of spatiotemporally inhomogeneous chemical and physical properties in a system is gaining attention across disciplines due to their resemblance in environmental and biological heterogeneity. Notably, origin of natural pH...

Chemical gradient sensing behavior of catalytically active colloids and enzymes is an area of immense interest owing to their importance in understanding fundamental spatiotemporal complexity patterns in living systems and designing dynamic materials. Herein, we have shown the peroxidase activity of DNAzyme (G‐quadruplex‐hemin complex tagged in a micron‐sized glass bead) can be modulated by metal ions and metal ion‐binding oligonucleotides. Next we demonstrated both experimentally and theoretically, that the localization and product formation ability of the DNAzyme‐containing particle remains biased to the more catalytically active zone where the concentration of metal ion (Hg2+) inhibitor is low. Interestingly, this biased localization can be broken by introduction of Hg2+ binding oligonucleotide in the system. Additionally, a macroscopically asymmetric catalytic product distributed zone has been achieved with this process, showing the possibility of regulation in autonomous spatially controlled chemical processes. This demonstration of autonomous modulation of the localization pattern and spatially specific enhanced product forming ability of DNAzymes will further enable the design of responsive nucleic acid‐based motile materials and surfaces.

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