Controlling the size, shape and stability of supramolecular polymers in water.
For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult. At the same time, the ability to do so is highly important in view of a number of applications in functional soft matter including electronics, biomedical engineering, and sensors. In the past, successful strategies to control the size and shape of supramolecular polymers typically focused on the use of templates, end cappers or selective solvent techniques. Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing electrostatic repulsive interactions on the hydrophilic rim and attractive non-covalent forces within the hydrophobic core of the polymerizing building block, we manage to create small and discrete spherical objects. Increasing the salt concentration to screen the charges induces a sphere-to-rod transition. Intriguingly, this transition is expressed in an increase of cooperativity in the temperature-dependent self-assembly mechanism, and more stable aggregates are obtained. For our study we select a benzene-1,3,5-tricarboxamide (BTA) core connected to a hydrophilic metal chelate via a hydrophobic, fluorinated L-phenylalanine based spacer (Scheme 1). The metal chelate selected is a Gd(III)-DTPA complex that contains two overall remaining charges per complex and necessarily two counter ions. The one-dimensional growth of the aggregate is directed by π-π stacking and intermolecular hydrogen bonding. However, the electrostatic, repulsive forces that arise from the charges on the Gd(III)-DTPA complex start limiting the one-dimensional growth of the BTA-based discotic once a certain size is reached. At millimolar concentrations the formed aggregate has a spherical shape and a diameter of around 5 nm as inferred from (1)H-NMR spectroscopy, small angle X-ray scattering, and cryogenic transmission electron microscopy (cryo-TEM). The strength of the electrostatic repulsive interactions between molecules can be reduced by increasing the salt concentration of the buffered solutions. This screening of the charges induces a transition from spherical aggregates into elongated rods with a length > 25 nm. Cryo-TEM allows to visualise the changes in shape and size. In addition, CD spectroscopy permits to derive the mechanistic details of the self-assembly processes before and after the addition of salt. Importantly, the cooperativity -a key feature that dictates the physical properties of the produced supramolecular polymers- increases dramatically upon screening the electrostatic interactions. This increase in cooperativity results in a significant increase in the molecular weight of the formed supramolecular polymers in water.
Organic Chemistry Institute and CeNTech, Westfälische Wilhelms-Universität Münster.
Pol
P
Besenius
Isja
I
de Feijter
Nico A J M
NA
Sommerdijk
Paul H H
PH
Bomans
Anja R A
AR
Palmans
D001549:Benzamides / Q000737:chemistry*; D002614:Chelating Agents / Q000737:chemistry; D002942:Circular Dichroism; D020285:Cryoelectron Microscopy / Q000379:methods; D019786:Gadolinium DTPA / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D046529:Microscopy, Electron, Transmission / Q000379:methods; D008958:Models, Molecular; D010649:Phenylalanine / Q000031:analogs & derivatives* / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D001549:Benzamides; D002614:Chelating Agents; C558700:benzene-1,3,5-tricarboxamide; D014867:Water; D010649:Phenylalanine; D019786:Gadolinium DTPA