A Self-Organizing Chemical Assembly Line

Abstract

Chemical syntheses generally involve a series of discrete transformations whereby a simple set of starting materials are progressively rendered more complex. In contrast, living systems accomplish their syntheses within complex chemical mixtures, wherein the self-organization of biomolecules allows them to form "assembly lines" that transform simple starting materials into more complex products. Here we demonstrate the functioning of an abiological chemical system whose simple parts self-organize into a complex system capable of directing the multistep transformation of the small molecules furan, dioxygen, and nitromethane into a more complex and information-rich product. The novel use of a self-assembling container molecule to catalytically transform a high-energy intermediate is central to the system's functioning.

Regulating signal enhancement with coordination-coupled deprotonation of a hydrazone switch

“…6 However, in most cases the signaling event in such processes relies on one input leading to one output, which is not suitable for designing multicomponent signaling networks. 3 In order to expand the scope of our system ( i.e. , using a single input in generating multiple outputs) and show its ability to reversibly control a catalytic process we explored the potential of coupling the CCD initiated signaling event with an amplification mechanism.…”

“…1 This complex signaling network is regulated by reversible feedback mechanisms that switch their activity “on” and “off” to maintain homeostasis. 2 Recently, there has been interest in designing multicomponent systems 3 that use signaling cascades, whereupon one molecule acts as the input to another, as a method towards mimicking the complexity 4 of biological processes. Such research is expected to shed light on the origins of life, 5 and lead to molecular computing, 6 and systems chemistry, 7 among other developments.…”

Stepwise Construction of Self‐Assembled Heterometallic Cages Showing High Proton Conductivity

“…[18] Non-hydrogen atoms were refined with anisotropic displacement coefficients. Due to the presence of highly disordered solvents, refinements of all complexes (CoL,1a,2a,2b,3a,and 3b)were carried out with constraints on afew bond distances, fixed using the DFIX command, and final refinements were performed with the modification of the structure factors for the electron densities of the solvent molecules using the SQUEEZE option of PLATON. Due to the presence of highly disordered solvents, refinements of all complexes (CoL,1a,2a,2b,3a,and 3b)were carried out with constraints on afew bond distances, fixed using the DFIX command, and final refinements were performed with the modification of the structure factors for the electron densities of the solvent molecules using the SQUEEZE option of PLATON.…”

“…Hydrogen atoms were assigned isotropic displacement coefficients, U(H) = 1.2U(C) or 1.5U (C-methyl), and respective coordinates were allowed to ride on their corresponding carbons. Due to the presence of highly disordered solvents, refinements of all complexes (CoL,1a,2a,2b,3a,and 3b)were carried out with constraints on afew bond distances, fixed using the DFIX command, and final refinements were performed with the modification of the structure factors for the electron densities of the solvent molecules using the SQUEEZE option of PLATON. Crystallographic data and refinement parameters are provided in Ta ble S1, and the important bond parameters are assembled in Ta ble S2 (Supporting Information).…”

Direct Synthesis of Controlled‐Size Nanospheres inside Nanocavities of Self‐Organized Photopolymerizing Soft Oxometalates [PW12O40]n (n=1100–7500)

“…Recently, POMs have been self‐assembled into their superstructures with soft‐matter properties (SOMs) . It may also be mentioned that very recently “a self‐organizing chemical assembly line” and a light‐driven POM shuttle in homogeneous catalysis have been reported . SOM macroions based on paddle‐wheel POMs have extended the coordination chemistry of POMs to soft matter and present new opportunities.…”