Emergent Behaviors in Kinetically Controlled Dynamic Self-Assembly of Synthetic Molecular Systems

Abstract

Living systems are categorically a kinetic state of matter that exhibits complex functions and emergent behaviors. By contrast, synthetic systems are relatively simple and are typically controlled by the thermodynamic parameters. To understand this inherent difference between the biological and synthetic systems, novel approaches are of vital importance. In this regard, we have designed a three-component molecular system (a triad) by conjugating an amino acid with two functional molecules (naphthalenediimide and pyrene), which facilitates kinetically controlled self-assemblies. Herein, we describe three different molecular aggregation states of triads (entitled State I, State II, and State III) and also the dynamic pathway complexities associated with their transformations from one state to another. By meticulously employing the triads of different molecular aggregation states and the stereochemical information of the amino acid, we report emergent behaviors termed “supramolecular speciation” and “supramolecular regulation”. Further, we present a hitherto unknown emergent property in a self-assembled state under the majority-rules experiment, which has been termed “super-nonlinearity”. This work provides novel insights into complex synthetic systems having unprecedented functions and properties. Such emergent behaviors of synthetic triads that involve an interplay among complex interactions may find relevance in the context of prebiotic chemical evolution.

Gold Nanoparticle Formation Kinetics and Mechanism: A Critical Analysis of the “Redox Crystallization” Mechanism

“…The FW 2-step mechanism currently enjoys very broad, expanding application in many parts of the natural world, including to multiple metal nanoparticle formation systems − including gold nanoparticles, homogeneous catalyst formation, − heterogeneous catalyst formation, catalyst sintering phenomena, protein aggregation, ,,, solid-state kinetics, , dye aggregation, and other areas of nature . The strengths of the 2-step mechanism and multiple insights it allows are summarized elsewhere for the interested reader, as are the weaknesses and caveats of the deliberately minimalistic, deliberately Ockham’s-razor-obeying, FW 2-step mechanismcaveats and weaknesses that anyone using our mechanism needs to understand in order to use it properly.…”

“…If totally different, it would be an important advance in the mechanisms of nanoparticle nucleation and growth. Indeed, a totally different mechanism hidden under identical mathematics would, if correct, be of broad importance to both kinetics and mechanisms, in general, and specifically to nucleation and growth across nature given the broad range of sigmoidal curves accounted for at present by the FW 2-step mechanism. ,,,− …”

Particle formation mechanisms supported by in situ synchrotron XAFS and SAXS studies: a review of metal, metal-oxide, semiconductor and selected other nanoparticle formation reactions

“…The first, disproof-based minimum mechanism for particle formation mechanism composed of specific pseudoelementary steps (that also add up to an experimentally demonstrated balanced reaction to well-characterized products) did not appear until 1997, 54 the 2-step mechanism of continuous nucleation and autocatalytic surface growth listed in Table 1. This simplest version of particle formation has since been used to successfully fit homogeneous nanoparticle formation, 178 heterogeneous nanoparticle formation, 179 solid state kinetics, 180 dye aggregation, 181 protein aggregation, 182 and other ''cooperative'' autocatalytic phenomena in nature. 183 Six upgraded, themselves deliberately minimum mechanisms for particle formation have since been reported 39,54,67,68,80,[184][185][186][187] as summarized in Table 1.…”

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)IrI·HPO4]2}2–

“…The two-pseudoelementary-step, minimalistic mechanism is known as the Finke–Watzky (FW) two-step mechanism and has found a broad and still expanding appeal in over 530 SciFinder citations at present, including in the following nanoparticle formation systems: Ir(0), ,, Rh(0), − Pt(0), , Ru(0), Pd(0), , Ni(0), Ag(0), , and Au(0) nanoparticles. Direct X-ray absorption fine structure (XAFS) support for the two-step mechanism exists in the cases of Rh(0) and Pt(0) nanoparticles, and direct small-angle X-ray scattering (SAXS) support for the two-step mechanism exists in the case of important work on Ni(0) nanoparticle formation. , Additional application of the FW two-step mechanism includes: homogeneous catalyst formation, − heterogeneous catalyst formation, − protein aggregation, − solid-state kinetics, , dye aggregation, and other areas of nature showing “cooperative” autocatalytic phenomena . Clearly, nucleation is slow and continuous, A → B, in many cases in nature, the opposite of classical nucleation theory and the LaMer model that posits putative “instantaneous (burst)” nucleation and “diffusion-controlled” growth.…”