In Operando Observation of Neuropeptide Capture and Release on Graphene Field-Effect Transistor Biosensors with Picomolar Sensitivity.

Transmission electron microscopy (TEM) is being pushed to new capabilities which enable studies on systems that were previously out of reach. Among recent innovations, TEM through liquid cells (LC-TEM) enables in operando observation of biological phenomena. This work applies LC-TEM to the study of biological components as they interact on an abiotic surface. Specifically, analytes or target molecules like neuropeptide Y (NPY) are observed in operando on functional graphene field-effect transistor (GFET) biosensors. Biological recognition elements (BREs) identified using biopanning with affinity to NPY are used to functionalize graphene to obtain selectivity. On working devices capable of achieving picomolar responsivity to neuropeptide Y, LC-TEM reveals translational motion, stochastic positional fluctuations due to constrained Brownian motion, and rotational dynamics of captured analyte. Coupling these observations with the electrical responses of the GFET biosensors in response to analyte capture and/or release will potentially enable new insights leading to more advanced and capable biosensor designs.

Aqueous Assembly of Oxide and Fluoride Nanoparticles into 3D Microassemblies.

We demonstrate rapid [∼mm3/(h·L)] organic ligand-free self-assembly of three-dimensional, >50 µm single-domain microassemblies containing up to 107 individual aligned nanoparticles through a scalable aqueous process. Organization and alignment of aqueous solution-dispersed nanoparticles are induced by decreasing their pH-dependent surface charge without organic ligands, which could be temperature-sensitive or infrared light absorbing. This process is exhibited by transforming both dispersed iron oxide hydroxide nanorods and lithium yttrium fluoride nanoparticles into high packing density microassemblies. The approach is generalizable to nanomaterials with pH-dependent surface charge (e.g., oxides, fluorides, and sulfides) for applications requiring long-range alignment of nanostructures as well as high packing density.

Mini Monomer Encapsulated Emulsion Polymerization of PMMA Using Aqueous ARGET ATRP.

A new emulsion polymerization based on Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) has been developed to produce poly(methyl methacrylate) (PMMA). The critical components of single-pot synthesis via a mini Monomer Encapsulated ARGET ATRP emulsion polymerization will be discussed. In this method, monomer is isolated in a micelle by pre-emulsification in a nonionic surfactant through high power stirring while acetone is introduced to the polymerization to aid in reactant transport and tetrabutylammonium salts are used as phase transfer agents. Polymerizations using tetrabutylammonium bromide (TBAB) were more controlled and demonstrated low D (Mw/Mn < 1.17), where those using tetrabutylammonium chloride (TBAC) exhibited higher D (Mw/Mn > 1.50). First-order linear kinetics for MMA polymerizations at 100 mM TBAB was demonstrated, while the reactions deviated from linearity at higher concentrations of TBAB and all concentrations of TBAC.

Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes.

Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEGn, where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG16, self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters <5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved Pt-PEG16 complex, underwent elongation in a "living supramolecular polymerization" process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore "static" with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG16), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.

Highly Concentrated Seed-Mediated Synthesis of Monodispersed Gold Nanorods.

The extremely large optical extinction coefficient of gold nanorods (Au-NRs) enables their use in a diverse array of technologies, rnging from plasmonic imaging, therapeutics and sensors, to large area coatings, filters, and optical attenuators. Development of the latter technologies has been hindered by the lack of cost-effective, large volume production. This is due in part to the low reactant concentration required for symmetry breaking in conventional seed-mediated synthesis. Direct scale up of laboratory procedures has limited viability because of excessive solvent volume, exhaustive postsynthesis purification processes, and the generation of large amounts of waste (e.g., hexadecyltrimethylammonium bromide(CTAB)). Following recent insights into the growth mechanism of Au-NRs and the role of seed development, we modify the classic seed-mediated synthesis via temporal control of seed and reactant concentration to demonstrate production of Au-NRs at more than 100-times the conventional concentration, while maintaining independent control and narrow distribution of nanoparticle dimensions, aspect ratio, and volume. Thus, gram scale synthesis of Au-NRs with prescribed aspect ratio and volume is feasible in a 100 mL reactor with 1/100th of organic waste relative to conventional approaches. Such scale-up techniques are crucial to cost-effectively meet the increased demand for large quantities of Au-NRs in emerging applications.

Complex and Hierarchical 2D Assemblies via Crystallization-Driven Self-Assembly of Poly(l-lactide) Homopolymers with Charged Termini.

Poly(l-lactide) (PLLA)-based nanoparticles have attracted much attention with respect to applications in drug delivery and nanomedicine as a result of their biocompatibility and biodegradability. Nevertheless, the ability to prepare PLLA assemblies with well-defined shape and dimensions is limited and represents a key challenge. Herein we report access to a series of monodisperse complex and hierarchical colloidally stable 2D structures based on PLLA cores using the seeded growth, "living-crystallization-driven self-assembly" method. Specifically, we describe the formation of diamond-shaped platelet micelles and concentric "patchy" block co-micelles by using seeds of the charge-terminated homopolymer PLLA24[PPh2Me]I to initiate the sequential growth of either additional PLLA24[PPh2Me]I or a crystallizable blend of the latter with the block copolymer PLLA42-b-P2VP240, respectively. The epitaxial nature of the growth processes used for the creation of the 2D block co-micelles was confirmed by selected area electron diffraction analysis. Cross-linking of the P2VP corona of the peripheral block in the 2D block co-micelles using Pt nanoparticles followed by dissolution of the interior region in good solvent for PLLA led to the formation of novel, hollow diamond-shaped assemblies. We also demonstrate that, in contrast to the aforementioned results, seeded growth of the unsymmetrical PLLA BCPs PLLA42-b-P2VP240 or PLLA20-b-PAGE80 alone from 2D platelets leads to the formation of diamond-fiber hybrid structures.

Uniform "Patchy" Platelets by Seeded Heteroepitaxial Growth of Crystallizable Polymer Blends in Two Dimensions.

Rectangular platelets formed by the self-assembly of block copolymers in selective solvents are of interest for a range of applications. Recently, we showed that the seeded growth of crystallizable blends of a block copolymer and homopolymer yields well-defined, low area dispersity examples of these two-dimensional (2D) structures. The key feature was the use of the same crystallizable polymer segment in the seed and blend components to enable an efficient homoepitaxial growth process. Herein we demonstrate that this 2D crystallization-driven self-assembly approach can be extended to heteroepitaxial growth by the use of different crystallizable polymers with compatible crystal structures. This allows the formation of well-defined "patchy" rectangular platelets and platelet block comicelles with different core chemistries. The use of scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy provided key information on the spatial location of the components in the resulting assemblies and thereby valuable insight into the 2D heteroepitaxial growth process.

Two-dimensional assemblies from crystallizable homopolymers with charged termini.

The creation of shaped, uniform and colloidally stable two-dimensional (2D) assemblies by bottom-up methods represents a challenge of widespread current interest for a variety of applications. Herein, we describe the utilization of surface charge to stabilize self-assembled planar structures that are formed from crystallizable polymer precursors by a seeded growth approach. Addition of crystallizable homopolymers with charged end-groups to seeds generated by the sonication of block copolymer micelles with crystalline cores yields uniform platelet micelles with controlled dimensions. Significantly, the seeded growth approach is characterized by a morphological memory effect whereby the origin of the seed, which can involve a quasi-hexagonal or rectangular 2D platelet precursor, dictates the observed 2D platelet shape. This new strategy is illustrated using two different polymer systems, and opens the door to the construction of 2D hierarchical structures with broad utility.

Redox Exfoliation of Layered Transition Metal Dichalcogenides.

Transition metal dichalcogenides (TMDs) have attracted considerable attention in a diverse array of applications due to the breadth of possible property suites relative to other low-dimensional nanomaterials (e.g., graphene, aluminosilicates). Here, we demonstrate an alternative methodology for the exfoliation of bulk crystallites of group V-VII layered TMDs under quiescent, benchtop conditions using mild redox chemistry. Anionic polyoxometalate species generated from edge sites adsorb to the TMD surface and create Coulombic repulsion that drives layer separation without the use of shear forces. This method is generalizable (MS2, MSe2, and MTe2) and effective in preparing high-concentration (>1 mg/mL) dispersions with narrow layer thickness distributions more rapidly and with safer reagents than alternative solution-based approaches. Finally, exfoliation of these TMDs is demonstrated in a range of solvent systems that were previously inaccessible due to large surface energy differences. These characteristics could be beneficial in the preparation of high-quality films and monoliths.