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The spontaneous assembly of chiral structures from building blocks that lack chirality is fundamentally important for colloidal chemistry and has implications for the formation of advanced optical materials. Here, we find that purified achiral gold tetrahedron-shaped nanoparticles assemble into two-dimensional superlattices that exhibit planar chirality under a balance of repulsive electrostatic and attractive van der Waals and depletion forces. A model accounting for these interactions shows that the growth of planar structures is kinetically preferred over similar three-dimensional products, explaining their selective formation. Exploration and mapping of different packing symmetries demonstrates that the hexagonal chiral phase forms exclusively because of geometric constraints imposed by the presence of constituent tetrahedra with sharp tips. A formation mechanism is proposed in which the chiral phase nucleates from within a related 2D achiral phase by clockwise or counterclockwise rotation of tetrahedra about their central axis. These results lay the scientific foundation for the high-throughput assembly of planar chiral metamaterials. The formation of nanostructures with chiral symmetry often requires chiral directing agents at a smaller length scale. Here, the authors report the self-assembly of 2D chiral superlattices from achiral tetrahedron-shaped building blocks.

In molecular systems, valency describes the number of bonds an atom can make with its neighbors. Larger objects such as colloids can be linked together to make connected structures in which the number of connections, or valency, is controlled by the central object. Jones et al. review the two main approaches to creating stiff bonds, based on DNA-based materials synthesis. These approaches allow the construction of molecular-like objects from building blocks much larger than single atoms. Science , this issue 10.1126/science.1260901 For over half a century, the biological roles of nucleic acids as catalytic enzymes, intracellular regulatory molecules, and the carriers of genetic information have been studied extensively. More recently, the sequence-specific binding properties of DNA have been exploited to direct the assembly of materials at the nanoscale. Integral to any methodology focused on assembling matter from smaller pieces is the idea that final structures have well-defined spacings, orientations, and stereo-relationships. This requirement can be met by using DNA-based constructs that present oriented nanoscale bonding elements from rigid core units. Here, we draw analogy between such building blocks and the familiar chemical concepts of “bonds” and “valency” and review two distinct but related strategies that have used this design principle in constructing new configurations of matter.

Whether two species will co-crystallize depends on the chemical, physical and structural complementarity of the interacting components. Here, by using DNA as a surface ligand, we selectively co-crystallize mixtures of two different anisotropic nanoparticles and systematically investigate the effects of nanoparticle size and shape complementarity on the resultant crystal symmetry, microstrain, and effective ‘DNA bond’ length and strength. We then use these results to understand a more complicated system where both size and shape complementarity change, and where one nanoparticle can participate in multiple types of directional interactions. Our findings offer improved control of non-spherical nanoparticles as building blocks for the assembly of sophisticated macroscopic materials, and provide a framework to understand complementarity and directional interactions in DNA-mediated nanoparticle crystallization. The structural properties of the DNA-mediated assembly of co-crystals of anisotropic nanoparticles can be controlled through the shape and size complementarity of the DNA-coated nanoparticles.

Multicomponent nanocrystal superlattices represent an interesting class of material that derives emergent properties from mesoscale structure, yet their programmability can be limited by the alkyl-chain-based ligands decorating the surfaces of the constituent nanocrystals. Polymeric ligands offer distinct advantages, as they allow for more precise tuning of the effective size and ‘interaction softness’ through changes to the polymer’s molecular weight, chemical nature, architecture, persistence length and surrounding solvent. Here we show the formation of 10 different binary nanocrystal superlattices (BNSLs) with both two- and three-dimensional order through independent adjustment of the core size of spherical nanocrystals and the molecular weight of densely grafted polystyrene ligands. These polymer-brush-based ligands introduce new energetic contributions to the interparticle potential that stabilizes various BNSL phases across a range of length scales and interparticle spacings. Our study opens the door for nanocrystals to become modular elements in the design of functional particle brush solids with controlled nanoscale interfaces and mesostructures. Binary nanocrystal superlattice metamaterials are arousing significant interest due to their potential for use in functional devices. Here, the authors endow the nanoparticles with polymer brushes which enable control over their spacings and thus mesoscale structure and properties.

A polymer pore template can control the order of assembly of nanoparticles into well-defined stacks and create superlattices. Lin et al. used DNA strands on gold nanoparticles to control interparticle distance. The DNA strands contained modified adenines with more rigid ribose groups that formed stronger base pairs. The height of the stacks of three different types of gold nanoparticle could be changed with different solvents, which in turn changed their optical response. Science , this issue p. 669 Locked DNA strands and micropores are used to assemble nanoparticles with different sizes and shapes into superlattices. DNA programmable assembly has been combined with top-down lithography to construct superlattices of discrete, reconfigurable nanoparticle architectures on a gold surface over large areas. Specifically, the assembly of individual colloidal plasmonic nanoparticles with different shapes and sizes is controlled by oligonucleotides containing “locked” nucleic acids and confined environments provided by polymer pores to yield oriented architectures that feature tunable arrangements and independently controllable distances at both nanometer- and micrometer-length scales. These structures, which would be difficult to construct by other common assembly methods, provide a platform to systematically study and control light-matter interactions in nanoparticle-based optical materials. The generality and potential of this approach are explored by identifying a broadband absorber with a solvent polarity response that allows dynamic tuning of visible light absorption.

Numerous mechanisms have been studied for chemical reactions to provide quantitative predictions on how atoms spatially arrange into molecules. In nanoscale colloidal systems, however, less is known about the physical rules governing their spatial organization, i.e., self-assembly, into functional materials. Here, we monitor real-time self-assembly dynamics at the single nanoparticle level, which reveal marked similarities to foundational principles of polymerization. Specifically, using the prototypical system of gold triangular nanoprisms, we show that colloidal self-assembly is analogous to polymerization in three aspects: ensemble growth statistics following models for step-growth polymerization, with nanoparticles as linkable “monomers”; bond angles determined by directional internanoparticle interactions; and product topology determined by the valency of monomeric units. Liquid-phase transmission electron microscopy imaging and theoretical modeling elucidate the nanometer-scale mechanisms for these polymer-like phenomena in nanoparticle systems. The results establish a quantitative conceptual framework for self-assembly dynamics that can aid in designing future nanoparticle-based materials. Few models exist that describe the spontaneous organization of colloids into materials. Here, the authors combine liquid-phase TEM and single particle tracking to observe the dynamics of gold nanoprisms, finding that nanoscale self-assembly can be understood within the framework of atomic polymerization.

Snowshoe hares molt from a brown coat to a white coat in winter. In some populations, however, where winter snow is less extensive, hares molt from a brown coat to a brown coat. Jones et al. show that regulation of the pigmentation gene Agouti is responsible for the winter coat color change. Hybridization with jackrabbits has led to introgression around this gene that facilitates the brown winter morph. Hybridization appears to have provided important adaptive variation to the snowshoe hare. Science , this issue p. 1355 Exchange of genetic variants through hybridization can seed past and ongoing adaptation to rapidly changing environments. Snowshoe hares ( Lepus americanus ) maintain seasonal camouflage by molting to a white winter coat, but some hares remain brown during the winter in regions with low snow cover. We show that cis-regulatory variation controlling seasonal expression of the Agouti gene underlies this adaptive winter camouflage polymorphism. Genetic variation at Agouti clustered by winter coat color across multiple hare and jackrabbit species, revealing a history of recurrent interspecific gene flow. Brown winter coats in snowshoe hares likely originated from an introgressed black-tailed jackrabbit allele that has swept to high frequency in mild winter environments. These discoveries show that introgression of genetic variants that underlie key ecological traits can seed past and ongoing adaptation to rapidly changing environments.

In this Perspective, we present a framework that defines how to understand and control material structure across length scales with inorganic nanoparticles. Three length scales, frequently discussed separately, are unified under the topic of hierarchical organization: atoms arranged into crystalline nanoparticles, ligands arranged on nanoparticle surfaces, and nanoparticles arranged into crystalline superlattices. Through this lens, we outline one potential pathway toward perfect colloidal matter that emphasizes the concept of uniformity. Uniformity is of both practical and functional importance, necessary to increase structural sophistication and realize the promise of nanostructured materials. Thus, we define the nature of nonuniformity at each length scale as a means to guide ongoing research efforts and highlight potential problems in the field.

Chemists have developed mechanistic insight into numerous chemical reactions by thoroughly characterizing nonequilibrium species. Although methods to probe these processes are well established for molecules, analogous techniques for understanding intermediate structures in nanomaterials have been lacking. We monitor the shape evolution of individual anisotropic gold nanostructures as they are oxidatively etched in a graphene liquid cell with a controlled redox environment. Short-lived, nonequilibrium nanocrystals are observed, structurally analyzed, and rationalized through Monte Carlo simulations. Understanding these reaction trajectories provides important fundamental insight connecting high-energy nanocrystal morphologies to the development of kinetically stabilized surface features and demonstrates the importance of developing tools capable of probing short-lived nanoscale species at the single-particle level.

Barrier tissues are populated by functionally plastic CD4 + resident memory T (T RM ) cells. Whether the barrier epithelium regulates CD4 + T RM cell locations, plasticity and activities remains unclear. Here we report that lung epithelial cells, including distinct surfactant protein C (SPC) low MHC high epithelial cells, function as anatomically-segregated and temporally-dynamic antigen presenting cells. In vivo ablation of lung epithelial MHC-II results in altered localization of CD4 + T RM cells. Recurrent encounters with cognate antigen in the absence of epithelial MHC-II leads CD4 + T RM cells to co-express several classically antagonistic lineage-defining transcription factors, changes their cytokine profiles, and results in dysregulated barrier immunity. In addition, lung epithelial MHC-II is needed for surface expression of PD-L1, which engages its ligand PD-1 to constrain lung CD4 + T RM cell phenotypes. Thus, we establish epithelial antigen presentation as a critical regulator of CD4 + T RM cell function and identify epithelial-CD4 + T RM cell immune interactions as core elements of barrier immunity. The maintenance of T resident memory (T RM ) cells within pulmonary tissues is incompletely understood. Here the authors show that antigen presentation by lung epithelial cells maintains function and phenotype of pulmonary T RM cells within specific locational niches.