Harnessing Cytosine for Tunable Nanoparticle Self-Assembly Behavior Using Orthogonal Stimuli.

Nucleobases control the assembly of DNA, RNA, etc. due to hydrogen bond complementarity. By combining these unique molecules with state-of-the-art synthetic polymers, it is possible to form nanoparticles whose self-assembly behavior could be altered under orthogonal stimuli (pH and temperature). Herein, we report the synthesis of cytosine-containing nanoparticles via aqueous reversible addition-fragmentation chain transfer polymerization-induced self-assembly. A poly(N-acryloylmorpholine) macromolecular chain transfer agent (mCTA) was chain-extended with cytosine acrylamide, and a morphological phase diagram was constructed. By exploiting the ability of cytosine to form dimers via hydrogen bonding, the self-assembly behavior of cytosine-containing polymers was altered when performed under acidic conditions. Under these conditions, stable nanoparticles could be formed at longer polymer chain lengths. Furthermore, the resulting nanoparticles displayed different morphologies compared to those at pH 7. Additionally, particle stability post-assembly could be controlled by varying pH and temperature. Finally, small-angle X-ray scattering was performed to probe their dynamic behavior under thermal cycling.

Controlled node growth on the surface of polymersomes.

Incorporating nucleobases into synthetic polymers has proven to be a versatile method for controlling self-assembly. The formation of strong directional hydrogen bonds between complementary nucleobases provides a driving force that permits access to complex particle morphologies. Here, nucleobase pairing was used to direct the formation and lengthening of nodes on the outer surface of vesicles formed from polymers (polymersomes) functionalised with adenine in their membrane-forming domains. Insertion of a self-assembling short diblock copolymer containing thymine into the polymersome membranes caused an increase in steric crowding at the hydrophilic/hydrophobic interface, which was relieved by initial node formation and subsequent growth. Nano-objects were imaged by (cryo-)TEM, which permitted quantification of node coverage and length. The ability to control node growth on the surface of polymersomes provides a new platform to develop higher-order nanomaterials with tailorable properties.

Precise control over supramolecular nanostructures via manipulation of H-bonding in π-amphiphiles.

Self-assembled supramolecular architectures are ubiquitous in nature. A synchronized combination of dynamic noncovalent interactions is the major driving force in forming unique structures with high-precision control over the self-assembly of supramolecular materials. Herein, we have achieved programmable nanostructures by introducing single/multiple H-bonding units in a supramolecular building block. A diverse range of nanostructures can be generated in aqueous medium by subtly tuning the structure of π-amphiphiles. 1D-cylindrical micelles, 2D-nanoribbons and hollow nanotubes are produced by systematically varying the number of H-bonding units (0-2) in structurally near identical π-amphiphiles. Spectroscopic measurements revealed the decisive role of H-bonding units for different modes of molecular packing. We have demonstrated that a competitive self-assembled state (a kinetically controlled aggregation state and a thermodynamically controlled aggregation state) can be generated by fine tuning the number of noncovalent forces present in the supramolecular building blocks. The luminescence properties of conjugated dithiomaleimide (DTM) provided insight into the relative hydrophobicity of the core in these nanostructures. In addition, fluorescence turn-off in the presence of thiophenol enabled us to probe the accessibility of the hydrophobic core in these assembled systems toward guest molecules. Therefore the DTM group provides an efficient tool to determine the relative hydrophobicity and accessibility of the core of various nanostructures which is very rarely studied in supramolecular assemblies.

Anisotropic polymer nanoparticles with controlled dimensions from the morphological transformation of isotropic seeds.

Understanding and controlling self-assembly processes at multiple length scales is vital if we are to design and create advanced materials. In particular, our ability to organise matter on the nanoscale has advanced considerably, but still lags far behind our skill in manipulating individual molecules. New tools allowing controlled nanoscale assembly are sorely needed, as well as the physical understanding of how they work. Here, we report such a method for the production of highly anisotropic nanoparticles with controlled dimensions based on a morphological transformation process (MORPH, for short) driven by the formation of supramolecular bonds. We present a minimal physical model for MORPH that suggests a general mechanism which is potentially applicable to a large number of polymer/nanoparticle systems. We envision MORPH becoming a valuable tool for controlling nanoscale self-assembly, and for the production of functional nanostructures for diverse applications.