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.

A New Architecture for DNA-Templated Synthesis in Which Abasic Sites Protect Reactants from Degradation.

The synthesis of artificial sequence-defined polymers that match and extend the functionality of proteins is an important goal in materials science. One way of achieving this is to program a sequence of chemical reactions between precursor building blocks by means of attached oligonucleotide adapters. However, hydrolysis of the reactive building blocks has so far limited the length and yield of product that can be obtained using DNA-templated reactions.

Active elastocapillarity in soft solids with negative surface tension.

Active solids consume energy to allow for actuation, shape change, and wave propagation not possible in equilibrium. Whereas active interfaces have been realized across many experimental systems, control of three-dimensional (3D) bulk materials remains a challenge. Here, we develop continuum theory and microscopic simulations that describe a 3D soft solid whose boundary experiences active surface stresses.

Rigidochromism by imide functionalisation of an aminomaleimide fluorophore.

Fluorescent dyes that exhibit high solid state quantum yields and sensitivity to the mechanical properties of their local environment are useful for a wide variety of applications, but are limited in chemical diversity. We report a trityl-functionalised maleimide that displays rigidochromic behaviour, becoming highly fluorescent when immobilised in a solid matrix, while displaying negligible fluorescence in solution. Furthermore, the dye's quantum yield is shown to be sensitive to the nature of the surrounding matrix.

DNA-polymer conjugates the graft-through polymerisation of native DNA in water.

The direct, graft-through, ring-opening metathesis polymerisation (ROMP) of unprotected DNA macromonomers is reported. By tuning the polymerisation conditions, good control is achieved, enabling the rapid and efficient synthesis of DNA-containing bottlebrush copolymers, without the need for protection of the DNA bases.

Synthesis and applications of anisotropic nanoparticles with precisely defined dimensions.

Shape and size play powerful roles in determining the properties of a material; controlling these aspects with precision is therefore an important, fundamental goal of the chemical sciences. In particular, the introduction of shape anisotropy at the nanoscale has emerged as a potent way to access new properties and functionality, enabling the exploration of complex nanomaterials across a range of applications. Recent advances in DNA and protein nanotechnology, inorganic crystallization techniques, and precision polymer self-assembly are now enabling unprecedented control over the synthesis of anisotropic nanoparticles with a variety of shapes, encompassing one-dimensional rods, dumbbells and wires, two-dimensional and three-dimensional platelets, rings, polyhedra, stars, and more.

Elastomeric polyamide biomaterials with stereochemically tuneable mechanical properties and shape memory.

Biocompatible polymers are widely used in tissue engineering and biomedical device applications. However, few biomaterials are suitable for use as long-term implants and these examples usually possess limited property scope, can be difficult to process, and are non-responsive to external stimuli. Here, we report a class of easily processable polyamides with stereocontrolled mechanical properties and high-fidelity shape memory behaviour.

Deep Eutectic Solvents as Media for the Prebiotic DNA-Templated Synthesis of Peptides.

Translation of genetic information into peptide products is one of the fundamental processes of biology. How this occurred prebiotically, in the absence of enzyme catalysts, is an intriguing question. Nucleic acid-templated synthesis (NATS) promotes reactions by bringing building blocks tethered to complementary DNA strands into close proximity and has been shown to enable peptide synthesis without enzymes-it could therefore serve as a model for prebiotic translation of information stored in nucleic acid sequences into functional peptides.

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.

Microcalorimetry and fluorescence show stable peptide nucleic acid (PNA) duplexes in high organic content solvent mixtures.

The selectivity of nucleic acid hybridisation can be exploited to template chemical reactions, enabling materials discovery by chemical evolution. However, to date the range of reactions that can be used has been limited to those that are compatible with aqueous media, since the addition of organic co-solvents can have a large impact on the stability of nucleic acid duplexes. Peptide nucleic acids (PNAs) are promising in this regard because previous studies have suggested they may be stable as duplexes in high organic content solvent mixtures.

Glyco-Platelets with Controlled Morphologies via Crystallization-Driven Self-Assembly and Their Shape-Dependent Interplay with Macrophages.

Two-dimensional (2D) materials are of great significance to the materials community as a result of their high surface area and controllable surface properties. However, controlled preparation of biodegradable 2D structures with biological activity is difficult. In this work we demonstrate that by careful selection of building block structures and assembly conditions it is possible to use crystallization-driven self-assembly (CDSA) to assemble well-defined 2D nanostructures from poly(-lactide) (PLLA)-based diblock glycopolymers.

The Evolution of DNA-Templated Synthesis as a Tool for Materials Discovery.

Precise control over reactivity and molecular structure is a fundamental goal of the chemical sciences. Billions of years of evolution by natural selection have resulted in chemical systems capable of information storage, self-replication, catalysis, capture and production of light, and even cognition. In all these cases, control over molecular structure is required to achieve a particular function: without structural control, function may be impaired, unpredictable, or impossible.

Reversibly Manipulating the Surface Chemistry of Polymeric Nanostructures via a "Grafting To" Approach Mediated by Nucleobase Interactions.

"Grafting to" polymeric nanostructures or surfaces is a simple and versatile approach to achieve functionalization. Herein, we describe the formation of mixed polymer-grafted nanoparticles through a supramolecular "grafting to" method that exploits multiple hydrogen-bonding interactions between the thymine (T)-containing cores of preformed micelles and the complementary nucleobase adenine (A) of added diblock copolymers. To demonstrate this new "grafting to" approach, mixed-corona polymeric nanoparticles with different sizes were prepared by the addition of a series of complementary diblock copolymers containing thermoresponsive poly(-isopropylacrylamide) (PNIPAM) to a preformed micelle with a different coronal forming block, poly(4-acryloylmorpholine) (PNAM).

Efficient DNA-Polymer Coupling in Organic Solvents: A Survey of Amide Coupling, Thiol-Ene and Tetrazine-Norbornene Chemistries Applied to Conjugation of Poly(N-Isopropylacrylamide).

A range of chemistries were explored for the efficient covalent conjugation of DNA to poly(N-isopropylacrylamide) (poly(NIPAM)) in organic solvents. Amide coupling and thiol-ene Michael addition were found to be ineffective for the synthesis of the desired products. However, the inverse electron-demand Diels-Alder (DA) reaction between tetrazine (Tz) and norbornene (Nb) was found to give DNA-polymer conjugates in good yields (up to 40%) in organic solvents (N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone), and without the need for a catalyst.

Construction of DNA-polymer hybrids using intercalation interactions.

Reversible addition-fragmentation chain transfer (RAFT) polymerisation was used to produce a range of polymers terminated with an acridine group, which intercalates efficiently into dsDNA; the structure of the polymer determines the nature and strength of the interaction. Using a short 63 base pair dsDNA, discrete and well-defined DNA-polymer hybrid nanoparticles were formed, which were characterised by dynamic light scattering, small-angle X-ray scattering and atomic force microscopy.

"Giant surfactants" created by the fast and efficient functionalization of a DNA tetrahedron with a temperature-responsive polymer.

Copper catalyzed azide-alkyne cycloaddition (CuAAC) was employed to synthesize DNA block copolymers (DBCs) with a range of polymer blocks including temperature-responsive poly(N-isoproylacrylamide) (poly(NIPAM)) and highly hydrophobic poly(styrene). Exceptionally high yields were achieved at low DNA concentrations, in organic solvents, and in the absence of any solid support. The DNA segment of the DBC remained capable of sequence-specific hybridization: it was used to assemble a precisely defined nanostructure, a DNA tetrahedron, with pendant poly(NIPAM) segments.