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In this Perspective, we present a unique approach to the design and synthesis of giant molecules based on “nanoatoms” for engineering structures across multiple length scales and controlling their macroscopic properties. Herein, “nanoatoms” refer to shape-persistent molecular nanoparticles (MNPs) with precisely defined chemical structures and surface functionalities that can serve as elemental building blocks for the precision synthesis of giant molecules by methods such as sequential “click” approach. Typical “nanoatoms” include those MNPs based on fullerenes, polyhedral oligomeric silsesquioxanes, polyoxometalates, and folded globular proteins. The resulting giant molecules are precisely defined macromolecules. They include, but are not limited to, giant surfactants, giant shape amphiphiles, and giant polyhedra. Giant surfactants are polymer tail-tethered “nanoatoms” where the two components have drastic chemical differences to impart amphiphilicity. Giant shape amphiphiles not only are built up by covalently bonded MNPs of distinct shapes where the self-assembly is driven by chemical interactions but also are largely influenced by the packing constraints of each individual shape. Giant polyhedra are either made of a large MNP or by deliberately placing “nanoatoms” at the vertices of a polyhedron. In general, giant molecules capture the essential structural features of their small-molecule counterparts in many ways but possess much larger sizes. They are recognized in certain cases as size-amplified versions of those counterparts, and often, they bridge the gap between small molecules and traditional macromolecules. Highly diverse, thermodynamically stable and metastable hierarchal structures are commonly observed in the bulk, thin film, and solution states of these giant molecules. Controlled structural variations by precision synthesis further reveal a remarkable sensitivity of their self-assembled structures to the primary chemical structures. Unconventional nanostructures can be obtained in confined environments or through directed self-assembly. All the results demonstrate that MNPs are unique elements for macromolecular science, providing a versatile platform for engineering nanostructures that are not only scientifically intriguing but also technologically relevant.

Self-assembly of rigid building blocks with explicit shape and symmetry is substantially influenced by the geometric factors and remains largely unexplored. We report the selective assembly behaviors of a class of precisely defined, nanosized giant tetrahedra constructed by placing different polyhedral oligomeric silsesquioxane (POSS) molecular nanoparticles at the vertices of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces precise positional interactions and results in diverse selectively assembled, highly ordered supramolecular lattices including a Frank-Kasper A15 phase, which resembles the essential structural features of certain metal alloys but at a larger length scale. These results demonstrate the power of persistent molecular geometry with balanced enthalpy and entropy in creating thermodynamically stable supramolecular lattices with properties distinct from those of other self-assembling soft materials.

Triticum urartu (diploid, AA) is the progenitor of the A subgenome of tetraploid (Triticum turgidum, AABB) and hexaploid (Triticum aestivum, AABBDD) wheat. Genomic studies of T. urartu have been useful for investigating the structure, function and evolution of polyploid wheat genomes. Here we report the generation of a high-quality genome sequence of T. urartu by combining bacterial artificial chromosome (BAC)-by-BAC sequencing, single molecule real-time whole-genome shotgun sequencing , linked reads and optical mapping. We assembled seven chromosome-scale pseudomolecules and identified protein-coding genes, and we suggest a model for the evolution of T. urartu chromosomes. Comparative analyses with genomes of other grasses showed gene loss and amplification in the numbers of transposable elements in the T. urartu genome. Population genomics analysis of 147 T. urartu accessions from across the Fertile Crescent showed clustering of three groups, with differences in altitude and biostress, such as powdery mildew disease. The T. urartu genome assembly provides a valuable resource for studying genetic variation in wheat and related grasses, and promises to facilitate the discovery of genes that could be useful for wheat improvement.