title: Effect of H-Bonding on Order Amplification in the Growth of a Supramolecular Polymer in Water.
abstract: While a great deal of knowledge on the roles of hydrogen bonding and hydrophobicity in proteins has resulted in the creation of rationally designed and functional peptidic structures, the roles of these forces on purely synthetic supramolecular architectures in water have proven difficult to ascertain. Focusing on a 1,3,5-benzenetricarboxamide (BTA)-based supramolecular polymer, we have designed a molecular modeling strategy to dissect the energetic contributions involved in the self-assembly (electrostatic, hydrophobic, etc.) upon growth of both ordered BTA stacks and random BTA aggregates. Utilizing this set of simulations, we have unraveled the cooperative mechanism for polymer growth, where a critical size must be reached in the aggregates before emergence and amplification of order into the experimentally observed fibers. Furthermore, we have found that the formation of ordered fibers is favored over disordered aggregates solely on the basis of electrostatic interactions. Detailed analysis of the simulation data suggests that H-bonding is a major source of this stabilization energy. Experimental and computational comparison with a newly synthesized 1,3,5-benzenetricarboxyester (BTE) derivative, lacking the ability to form the H-bonding network, demonstrated that this BTE variant is also capable of fiber formation, albeit at a reduced persistence length. This work provides unambiguous evidence for the key 1D driving force of hydrogen bonding in enhancing the persistency of monomer stacking and amplifying the level of order into the growing supramolecular polymer in water. Our computational approach provides an important relationship directly linking the structure of the monomer to the structure and properties of the supramolecular polymer.
authors.affiliation: Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland , Galleria 2, Via Cantonale 2c, CH-6928 Manno, Switzerland.
authors.forename: Matteo
authors.initials: M
authors.lastname: Garzoni
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology , 5612 AZ Eindhoven, The Netherlands.|MERLN Institute for Technology-Inspired Regenerative Medicine, Maastricht University , P.O. Box 616, 6200 MD Maastricht, The Netherlands.
authors.forename: Matthew B
authors.initials: MB
authors.lastname: Baker
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology , 5612 AZ Eindhoven, The Netherlands.
authors.forename: Christianus M A
authors.initials: CMA
authors.lastname: Leenders
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology , 5612 AZ Eindhoven, The Netherlands.
authors.forename: Ilja K
authors.initials: IK
authors.lastname: Voets
authors.affiliation: Institute for Bioengineering of Catalonia (IBEC) , 08028 Barcelona, Spain.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Albertazzi
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology , 5612 AZ Eindhoven, The Netherlands.
authors.forename: Anja R A
authors.initials: ARA
authors.lastname: Palmans
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology , 5612 AZ Eindhoven, The Netherlands.
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer
authors.affiliation: Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland , Galleria 2, Via Cantonale 2c, CH-6928 Manno, Switzerland.
authors.forename: Giovanni M
authors.initials: GM
authors.lastname: Pavan