Chemically Fueled Dissipative Self‐Assembly that Exploits Cooperative Catalysis

• Published in: Angewandte Chemie 2019-01, Vol.131 (1), p.250-253
• Main Authors: Bal, Subhajit, Das, Krishnendu, Ahmed, Sahnawaz, Das, Dibyendu
• Format: Article
• Language: English
• Subjects: Assembly; Catalysis; Chemical fuels; Chemistry; Dismantling; Gele; Guanosine triphosphate; Histidine; Hydrolysis; Katalyse; Kooperative Effekte; Nucleoside triphosphates; Organic chemistry; Selbstorganisation; Substrates; Systemchemie
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201811749

In living systems, dissipative processes are driven by the endergonic hydrolysis of chemical fuels such as nucleoside triphosphates. Now, through a simple model system, a transient self‐assembled state is realized by utilizing the catalytic effect of histidine on the formation and breaking of ester bonds. First, histidine facilitates the ester bond formation, which then rapidly co‐assembles to form a self‐supporting gel. An out‐of‐equilibrium state is realized owing to the cooperative catalysis by the proximal histidines in the assembled state, driving the second pathway and resulting in disassembly to sol. Cooperative effects that use the dual role of imidazoles as nucleophile and as proton donor is utilized to achieve transient assemblies. This simple system mimics the structural journey seen in microtubule formation where the substrate GTP facilitates the non‐covalent assembly and triggers a cooperative catalytic process, leading to substrate hydrolysis and subsequent disassembly. Selbst ist das Molekül: Ein sich selbst ordnendes System erreicht einen Ungleichgewichtszustand durch Energieabgabe aus der aggregierten Strukturform. Dabei werden kooperative Effekte von nahe zueinander befindlichen Histidinmotiven genutzt, welche die Hydrolyse von Esterbindungen in einem Amphiphil mit Lipidkette katalysieren.