Comparative Analyses of a Family of Potential Self‐Replicators: The Subtle Interplay between Molecular Structure and the Efficacy of Self‐Replication

Abstract

It is envisioned that protocols based on self-replication will emerge as a formidable synthetic apparatus for the production of nanoscale assemblies through molecular structures that are capable of automultiplication with high reaction rates and selectivities. To achieve this goal, a complete understanding of the relationship between molecular structure and replication efficiency is necessary. Rigorous experimental and theoretical analyses of a series of self-complementary scaffolds that are intimately related in a constitutional sense, manufactured through the Diels-Alder reaction of complementary subunits, were undertaken. Experimental and computational methods were employed to map the key determinants that dictate the emergence of self-replicative function, as well as the efficiency, rate and selectivity of the self-replicative processes.

Fission Yeast Hsk1 (Cdc7) Kinase Is Required After Replication Initiation for Induced Mutagenesis and Proper Response to DNA Alkylation Damage

“…For example, in a recent proteomics study, budding yeast Cdc7 was isolated in an affinity purification using MGMT (O 6 -methylguanine-DNA methyltransferase (Niture et al 2005). This enzyme is responsible for directly removing methyl groups from DNA damaged by alkylating agents such as N-methyl-N-nitrosourea (MNU) (Kaina et al 2001(Kaina et al , 2007Wyatt and Pittman 2006); fission yeast uses a different enzyme to deal with these lesions (Pearson et al 2006). Therefore, we propose that Hsk1 may contribute to the choice of repair mechanism by direct regulation of repair proteins at the replication fork.…”

Mechanisms of Autocatalysis

“…Philp and co‐workers examined autocatalytic aspects of the Diels–Alder reaction between furans and maleimides in depth109–112 (Scheme ). This system is highly sensitive to structural variations: for example, a methylene group can be the difference between efficient autocatalysis and systems that suffer from competitive preassociative reactions 109…”

Mechanismen der Autokatalyse

“…[109][110][111][112] Das System ist hochempfindlich gegenüber Strukturveränderungen, so kann beispielsweise eine Methylengruppe den Unterschied ausmachen zwischen einer wirksamen Autokatalyse und Systemen, die konkurrierende Präassoziationsreaktionen erfahren. [109][110][111][112] Das System ist hochempfindlich gegenüber Strukturveränderungen, so kann beispielsweise eine Methylengruppe den Unterschied ausmachen zwischen einer wirksamen Autokatalyse und Systemen, die konkurrierende Präassoziationsreaktionen erfahren.…”

“…Philp und Mitarbeiter untersuchten ausführlich die autokatalytischen Aspekte der Diels-Alder-Reaktion zwischen Furanen und Maleinimiden (Schema 42). [109][110][111][112] Das System ist hochempfindlich gegenüber Strukturveränderungen, so kann beispielsweise eine Methylengruppe den Unterschied ausmachen zwischen einer wirksamen Autokatalyse und Systemen, die konkurrierende Präassoziationsreaktionen erfahren. [109]…”