Andrew J. Senesi

DNA-nanoparticle superlattices formed from anisotropic building blocks

Directional bonding interactions in solid-state atomic lattices dictate the unique symmetries of atomic crystals, resulting in a diverse and complex assortment of three-dimensional structures that exhibit a wide variety of material properties. Methods to create analogous nanoparticle superlattices are beginning to be realized, but the concept of anisotropy is still largely underdeveloped in most particle assembly schemes. Some examples provide interesting methods to take advantage of anisotropic effects, but most are able to make only small clusters or lattices that are limited in crystallinity and especially in lattice parameter programmability. Anisotropic nanoparticles can be used to impart directional bonding interactions on the nanoscale, both through face-selective functionalization of the particle with recognition elements to introduce the concept of valency, and through anisotropic interactions resulting from particle shape. In this work, we examine the concept of inherent shape-directed crystallization in the context of DNA-mediated nanoparticle assembly. Importantly, we show how the anisotropy of these particles can be used to synthesize one-, two- and three-dimensional structures that cannot be made through the assembly of spherical particles.

DNA-mediated nanoparticle crystallization into Wulff polyhedra

Crystallization is a fundamental and ubiquitous process much studied over the centuries. But although the crystallization of atoms is fairly well understood, it remains challenging to predict reliably the outcome of molecular crystallization processes that are complicated by various molecular interactions and solvent involvement. This difficulty also applies to nanoparticles: high-quality three-dimensional crystals are mostly produced using drying and sedimentation techniques that are often impossible to rationalize and control to give a desired crystal symmetry, lattice spacing and habit (crystal shape). In principle, DNA-mediated assembly of nanoparticles offers an ideal opportunity for studying nanoparticle crystallization: a well-defined set of rules have been developed to target desired lattice symmetries and lattice constants, and the occurrence of features such as grain boundaries and twinning in DNA superlattices and traditional crystals comprised of molecular or atomic building blocks suggests that similar principles govern their crystallization. But the presence of charged biomolecules, interparticle spacings of tens of nanometres, and the realization so far of only polycrystalline DNA-interconnected nanoparticle superlattices, all suggest that DNA-guided crystallization may differ from traditional crystal growth. Here we show that very slow cooling, over several days, of solutions of complementary-DNA-modified nanoparticles through the melting temperature of the system gives the thermodynamic product with a specific and uniform crystal habit. We find that our nanoparticle assemblies have the Wulff equilibrium crystal structure that is predicted from theoretical considerations and molecular dynamics simulations, thus establishing that DNA hybridization can direct nanoparticle assembly along a pathway that mimics atomic crystallization.

Small Angle X-ray Scattering for Nanoparticle Research

X-ray scattering is a structural characterization tool that has impacted diverse fields of study. It is unique in its ability to examine materials in real time and under realistic sample environments, enabling researchers to understand morphology at nanometer and angstrom length scales using complementary small and wide angle X-ray scattering (SAXS, WAXS), respectively. Herein, we focus on the use of SAXS to examine nanoscale particulate systems. We provide a theoretical foundation for X-ray scattering, considering both form factor and structure factor, as well as the use of correlation functions, which may be used to determine a particles size, size distribution, shape, and organization into hierarchical structures. The theory is expanded upon with contemporary use cases. Both transmission and reflection (grazing incidence) geometries are addressed, as well as the combination of SAXS with other X-ray and non-X-ray characterization tools. We conclude with an examination of several key areas of research where X-ray scattering has played a pivotal role, including in situ nanoparticle synthesis, nanoparticle assembly, and operando studies of catalysts and energy storage materials. Throughout this review we highlight the unique capabilities of X-ray scattering for structural characterization of materials in their native environment.

Establishing the design rules for DNA-mediated programmable colloidal crystallization

DNA-programmable colloidal crystals are assembled with 5–80 nm nanoparticles, and the lattice parameters of the resulting crystals vary from 25 to 225 nm. A predictable and mathematically definable relationship between particle size and DNA length dictates the assembly and crystallization processes, creating a set of design rules for DNA-based nanoscale assembly.

Assembly and organization processes in DNA-directed colloidal crystallization

We present an analysis of the key steps involved in the DNA-directed assembly of nanoparticles into crystallites and polycrystalline aggregates. Additionally, the rate of crystal growth as a function of increased DNA linker length, solution temperature, and self-complementary versus non-self-complementary DNA linker strands (1- versus 2-component systems) has been studied. The data show that the crystals grow via a 3-step process: an initial “random binding” phase resulting in disordered DNA-AuNP aggregates, followed by localized reorganization and subsequent growth of crystalline domain size, where the resulting crystals are well-ordered at all subsequent stages of growth.

Controlling the Lattice Parameters of Gold Nanoparticle FCC Crystals with Duplex DNA Linkers

DNA-functionalized gold nanoparticles can be used to induce the formation and control the unit cell parameters of highly ordered face-centered cubic crystal lattices. Nanoparticle spacing increases linearly with longer DNA interconnect length, yielding maximum unit cell parameters of 77 nm and 0.52% inorganic-filled space for the DNA constructs studied. In general, we show that longer DNA connections result in a decrease in the overall crystallinity and order of the lattice due to greater conformational flexibility.

Stepwise Evolution of DNA‐Programmable Nanoparticle Superlattices

Colloidal crystals can be assembled using a variety of entropic, depletion, electrostatic, or biorecognition forces and provide a convenient model system for studying crystal growth. Although superlattices with diverse geometries can be assembled in solution and on surfaces, the incorporation of specific bonding interactions between particle building blocks and a substrate would significantly enhance control over the growth process. Herein, we use a stepwise growth process to systematically study and control the evolution of a body-centered cubic (bcc) crystalline thinfilm comprised of nanoparticle building blocks functionalized with DNA on a complementary DNA substrate. We examine crystal growth as a function of temperature, number of layers, and substrate–particle bonding interactions. Importantly, the judicious choice of DNA interconnects allows one to tune the interfacial energy between various crystal planes and the substrate, and thereby control crystal orientation and size in a stepwise fashion using chemically programmable attractive forces. This is a unique approach since prior studies involving superlattice assembly typically rely on repulsive interactions between particles to dictate structure, and those that rely on attractive forces (e.g. ionic systems) still maintain repulsive particle–substrate interactions. In addition to providing a model for crystallization, the field of particle assembly has garnered considerable interest because materials generated from ordered particle arrays can have novel optical, 13–17] electronic, and magnetic properties. These properties can be sensitive to the composition, symmetry, and distance between nanoparticles, in addition to the number of layers and orientation. DNA-mediated nanoparticle crystallization is particularly attractive for preparing these materials because the nanoparticle building blocks can be considered a type of “programmable atom equivalent” with tailorable size, composition, shape, and bonding interactions. This tunability allows one to access a diverse class of crystal symmetries, tailor lattice parameters with sub-nanometer resolution, and create structures that have no known mineral equivalent. Indeed, to date, 17 unique symmetries have been realized and over 100 unique crystal structures have been synthesized, all of which conform to a key hypothesis: these atom equivalents assemble into structures that maximize the total number of hybridized DNA interconnects between particles. While these structures have enormous potential, their use is limited because they are typically formed in solution as polycrystalline aggregates with little control over crystal size or orientation. Consequently, it is difficult to measure their properties or integrate them with other device elements using existing microfabrication techniques. The development of thin-film superlattices is therefore necessary to fully realize the potential of these structures as metamaterials, photonic crystals, and data storage elements. The growth of DNA-mediated monoand multi-layered nanoparticle structures was first examined by our group and later by Niemeyer and co-workers. However, the use of strong DNA interactions prevented nanoparticle crystallization. Herein, we exploit multiple weak DNA interactions for superlattice growth to examine the development of crystal orientation (texture) and control film thickness. Body-centered cubic colloidal crystals composed of spherical nucleic acid gold nanoparticle conjugates (SNA-AuNPs) were used as a model system since these structures require two complementary particle types and therefore allow the stepwise introduction of each layer. Alternatively, other crystal symmetries such as face-centered cubic (fcc) require

One-Dimensional Nanorod Arrays: Independent Control of Composition, Length, and Interparticle Spacing with Nanometer Precision

We report the synthesis of solution dispersible, one-dimensional metal nanostructure arrays as small as 35 nm in diameter using on-wire lithography, wherein feature thickness and spacing in the arrays is tailorable down to approximately 6 and 1 nm, respectively. Using this unique level of control, we present solution-averaged extinction spectra of 35 nm diameter Au nanorod dimers with varying gap sizes to illustrate the effect of gap size on plasmon coupling between nanorods. Additionally, we demonstrate control over the composition of the arrays with Au, Ni, and Pt segments, representing important advances in controlling the ordering of sub-100 nm nanostructures that are not available with current synthesis or assembly methods.

Oligonucleotide flexibility dictates crystal quality in DNA-programmable nanoparticle superlattices.

The evolution of crystallite size and microstrain in DNA-mediated nanoparticle superlattices is dictated by annealing temperature and the flexibility of the interparticle bonds. This work addresses a major challenge in synthesizing optical metamaterials based upon noble metal nanoparticles by enabling the crystallization of large nanoparticles (100 nm diameter) at high volume fractions (34% metal).

Epitaxial Growth of DNA-Assembled Nanoparticle Superlattices on Patterned Substrates

DNA-functionalized nanoparticles, including plasmonic nanoparticles, can be assembled into a wide range of crystalline arrays via synthetically programmable DNA hybridization interactions. Here we demonstrate that such assemblies can be grown epitaxially on lithographically patterned templates, eliminating grain boundaries and enabling fine control over orientation and size of assemblies up to thousands of square micrometers. We also demonstrate that this epitaxial growth allows for orientational control, systematic introduction of strain, and designed defects, which extend the range of structures that can be made using superlattice assembly. Ultimately, this will open the door to integrating self-assembled plasmonic nanoparticle materials into on-chip optical or optoelectronic platforms.