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.

Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self-assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate-induced templating and cooperativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5-nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2-pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.

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...

Multivalent chemical fuel driven transient assembly plays a critical role in biological processes. This inspires chemists to design synthetic systems having transient and dynamic functionalities. However, a detailed understanding about the temporal evolution of each of the intermediate species in a multi‐step assembly under dissipative conditions has not yet been explored. Herein, we have shown under dissipative conditions, how the strength of dissipation can modulate the compositional behavior of each of the intermediate species during their survival period by using kinetic modeling (with Python). We have observed that the appearance and disappearance of intermediates (formed either at the first or penultimate assembly step) are highly non‐linear in nature, and it is possible to trap any of the desired intermediates or a mixture of them of certain compositions at a definite time interval simply by tuning the strength of dissipation.

Herein we report migrational behaviour and spatial distribution of calf thymus DNA in gradient of different physiologically relevant mono- and divalent cations in two different conditions – (i) microfluidic and...