Jennifer N. Cha

Biomimetic synthesis of ordered silica structures mediated by block copolypeptides

In biological systems such as diatoms and sponges, the formation of solid silica structures with precisely controlled morphologies is directed by proteins and polysaccharides and occurs in water at neutral pH and ambient temperature. Laboratory methods, in contrast, have to rely on extreme pH conditions and/or surfactants to induce the condensation of silica precursors into specific morphologies or patterned structures. This contrast in processing conditions and the growing demand for benign synthesis methods that minimize adverse environmental effects have spurred much interest in biomimetic approaches in materials science. The recent demonstration that silicatein—a protein found in the silica spicules of the sponge Tethya aurantia—can hydrolyse and condense the precursor molecule tetraethoxysilane to form silica structures with controlled shapes at ambient conditions seems particularly promising in this context. Here we describe synthetic cysteine-lysine block copolypeptides that mimic the properties of silicatein: the copolypeptides self-assemble into structured aggregates that hydrolyse tetraethoxysilane while simultaneously directing the formation of ordered silica morphologies. We find that oxidation of the cysteine sulphydryl groups, which is known to affect the assembly of the block copolypeptide, allows us to produce different structures: hard silica spheres and well-defined columns of amorphous silica are produced using the fully reduced and the oxidized forms of the copolymer, respectively.

Large-area spatially ordered arrays of gold nanoparticles directed by lithographically confined DNA origami

The development of nanoscale electronic and photonic devices will require a combination of the high throughput of lithographic patterning and the high resolution and chemical precision afforded by self-assembly. However, the incorporation of nanomaterials with dimensions of less than 10 nm into functional devices has been hindered by the disparity between their size and the 100 nm feature sizes that can be routinely generated by lithography. Biomolecules offer a bridge between the two size regimes, with sub-10 nm dimensions, synthetic flexibility and a capability for self-recognition. Here, we report the directed assembly of 5-nm gold particles into large-area, spatially ordered, two-dimensional arrays through the site-selective deposition of mesoscopic DNA origami onto lithographically patterned substrates and the precise binding of gold nanocrystals to each DNA structure. We show organization with registry both within an individual DNA template and between components on neighbouring DNA origami, expanding the generality of this method towards many types of patterns and sizes.

Biophysically Defined and Cytocompatible Covalently Adaptable Networks as Viscoelastic 3D Cell Culture Systems

Presented here is a cytocompatible covalently adaptable hydrogel uniquely capable of mimicking the complex biophysical properties of native tissue and enabling natural cell functions without matrix degradation. Demonstrated is both the ability to control elastic modulus and stress relaxation time constants by more than an order of magnitude while predicting these values based on fundamental theoretical understanding and the simulation of muscle tissue and the encapsulation of myoblasts.

Highly ordered multilayered 3D graphene decorated with metal nanoparticles

Highly ordered multi-layered three-dimensional (3D) graphene structures decorated with Pd, Pt and Au metal nanoparticles are prepared and characterized. The ability to control the morphology, distribution and size of the metal nanoparticles on the 3D graphene support upon changing the electro- and electroless-deposition conditions is demonstrated. Tailor-made Pt nanostructures, with nanospike and nanoparticle shapes, are prepared using electroless deposition techniques. Au nanoflowers and nanoparticle structures and Pd nanocubes are obtained following electrodeposition onto the 3D graphene support. The deposition patterns and trends are characterized. The greatly enhanced electrocatalytic activity of the metal-NP–graphene surfaces has been illustrated in connection to voltammetric measurements of ORR and hydrogen peroxide at 3D-graphene coated with Pt and Pd nanoparticles, respectively. Such metal nanoparticles decorated multi-layer 3D graphene allows for high mass transport access and catalytic activity for a diverse range of applications, including sensor and fuel-cell technologies.

Phase change nanodot arrays fabricated using a self-assembly diblock copolymer approach

Self-assembling diblock copolymer, polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP), was used as the template for fabricating phase change nanostructures. The high density GeSb nanodots were formed by etching into an amorphous GeSb thin film using silica hard mask which was patterned on top of polymer. The nanodot arrays are 15nm in diameter with 30nm spacing. This is smaller than most structures obtained by e-beam lithography. Time-resolved x-ray diffraction studies showed that the phase transition occurred at 235°C, which is 5°C lower than blanket GeSb film but higher than that of Ge2Sb2Te5 (150°C). GeSb showed good temperature stability for fabrication of small memory devices.

Aptamer‐Crosslinked Microbubbles: Smart Contrast Agents for Thrombin‐Activated Ultrasound Imaging

Thrombosis, or malignant blood clotting, is associated with numerous cardiovascular diseases and cancers. A microbubble contrast agent is presented that produces ultrasound harmonic signal only when exposed to elevated thrombin levels. Initially silent microbubbles are activated in the presence of both thrombin-spiked and freshly clotting blood in three minutes with detection limits of 20 nM thrombin and 2 aM microbubbles.

Enhanced Hydrogen Production from DNA‐Assembled Z‐Scheme TiO2–CdS Photocatalyst Systems

A wide range of inorganic nanostructures have been used as photocatalysts for generating H2. To increase activity, Z-scheme photocatalytic systems have been implemented that use multiple types of photoactive materials and electron mediators. Optimal catalysis has previously been obtained by interfacing different materials through aggregation or epitaxial nucleation, all of which lowers the accessible active surface area. DNA has now been used as a structure-directing agent to organize TiO2 and CdS nanocrystals. A significant increase in H2 production compared to CdS or TiO2 alone was thus observed directly in solution with no sacrificial donors or applied bias. The inclusion of benzoquinone (BQ) equidistant between the TiO2 and CdS through DNA assembly further increased H2 production. While the use of a second quinone in conjunction with BQ showed no more improvement, its location within the Z-scheme was found to strongly influence catalysis.

Solvent-based assembly of CdSe nanorods in solution.

We demonstrate a purely solvent-based approach to assembling CdSe nanorods into vertically aligned, hexagonally packed monolayers in solution. Nanorods were dispersed in a mixture of good solvent with high vapor pressure and bad solvent with low vapor pressure, and preferential evaporation of the good solvent led to ordered assembly under conditions of continuously decreasing solvent quality. No applied external bias, extensive control of drying conditions, exceptionally monodisperse nanoparticles, or high concentrations of additives were required. This clean and facile method yielded ordered nanorod sheets of up to 7.5 μm wide with potential use as active materials in unique applications.

50 nm DNA Nanoarrays Generated from Uniform Oligonucleotide Films

One of the most challenging but potentially rewarding goals in nanoscience is the ability to direct the assembly of nanoscale materials into functional architectures with high yields, minimal steps, and inexpensive procedures. Despite their unique physical properties, the inherent difficulties of engineering wafer-level arrays of useful devices from nanoscale materials in a cost-effective manner have provided serious roadblocks toward technological impact. To address nanoscale features while still maintaining low fabrication costs, we demonstrate here an inexpensive printing method that enables repeated patterning of large-area arrays of nanoscale materials. DNA strands were patterned over 4 mm areas with 50 nm resolution by a soft-lithographic subtraction printing process, and DNA hybridization was used to direct the assembly of sub-20 nm materials to create highly ordered two-dimensional nanoparticle arrays. The entire printing and assembly process was accomplished in as few as three fabrication steps and required only a single lithographically templated silicon master that could be used repeatedly. The low-cost procedures developed to generate nanoscale DNA patterns can be easily extended toward roll-to-roll assembly of nanoscale materials with sub-50 nm resolution and fidelity.

Highly ordered tailored three-dimensional hierarchical nano/microporous gold–carbon architectures

The preparation and characterization of three-dimensional hierarchical architectures, consisting of monolithic nanoporous gold or silver films formed on highly ordered 3D microporous carbon supports, are described. The formation of these nano/microporous structures involves the electrodeposition or sputtering of metal alloys onto the lithographically patterned multi-layered microporous carbon, followed by preferential chemical dealloying of the less noble component. The resulting hierarchical structure displays a highly developed 3D interconnected network of micropores with a nanoporous metal coating. Tailoring the nanoporosity of the metal films and the diameter of the large micropores has been accomplished by systematically changing the alloy compositions via control of the deposition potential, plating solution and coarsening time. SEM imaging illustrates the formation of unique biomimetic nanocoral- or nanocauliflower-like self-supporting structures, depending on the specific preparation conditions. The new 3D hierarchical nano/microporous architectures allow for enhanced mass transport and catalytic activity compared to common nanoporous films prepared on planar substrates. The functionality of this new carbon–gold hierarchical structure is illustrated for the greatly enhanced performance of enzymatic biofuel cells where a substantially higher power output is observed compared to the bare microporous carbon substrate.