Showing papers by "Christopher B. Murray published in 2020"

Emergence of complexity in hierarchically organized chiral particles

Abstract: The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.

Unusual Dinitrogen Binding and Electron Storage in Dinuclear Iron Complexes.

Abstract: A rare example of a dinuclear iron core with a non-linearly bridged dinitrogen ligand is reported in this work. One-electron reduction of [(tBupyrr2py)Fe(OEt2)] (1) (tBupyrr2py2- = 2,6-bis((3,5-di-tert-butyl)pyrrol-2-yl)pyridine) with KC8 yields the complex [K]2[(tBupyrr2py)Fe]2(μ2-η1:η1-N2) (2), where the unusual cis-divacant octahedral coordination geometry about each iron and the η5-cation-π coordination of two potassium ions with four pyrrolyl units of the ligand cause distortion of the bridging end-on μ-N2 about the FeN2Fe core. Attempts to generate a Et2O-free version of 1 resulted instead in a dinuclear helical dimer, [(tBupyrr2py)Fe]2 (3), via bridging of the pyridine moieties of the ligand. Reduction of 3 by two electrons under N2 does not break up the dimer, nor does it result in formation of 2 but instead formation of the ate-complex [K(OEt2)]2[(tBupyrr2py)Fe]2 (4). Reduction of 1 by two electrons and in the presence of crown-ether forms the tetraanionic N2 complex [K2][K(18-crown-6)]2(tBupyrr2py)Fe]2(μ2-η1:η1-N2) (5), also having a distorted FeN2Fe moiety akin to 2. Complex 2 is thermally unstable and loses N2, disproportionating to Fe nanoparticles among other products. A combination of single-crystal X-ray diffraction studies, solution and solid-state magnetic studies, and 57Fe Mossbauer spectroscopy has been applied to characterize complexes 2-5, whereas DFT studies have been used to help explain the bonding and electronic structure in these unique diiron-N2 complexes 2 and 5.

Simultaneous Photonic and Excitonic Coupling in Spherical Quantum Dot Supercrystals.

Abstract: Semiconductor nanocrystals, or quantum dots (QDs), simultaneously benefit from inexpensive low-temperature solution processing and exciting photophysics, making them the ideal candidates for next-generation solar cells and photodetectors. While the working principles of these devices rely on light absorption, QDs intrinsically belong to the Rayleigh regime and display optical behavior limited to electric dipole resonances, resulting in low absorption efficiencies. Increasing the absorption efficiency of QDs, together with their electronic and excitonic coupling to enhance charge carrier mobility, is therefore of critical importance to enable practical applications. Here, we demonstrate a general and scalable approach to increase both light absorption and excitonic coupling of QDs by fabricating hierarchical metamaterials. We assemble QDs into crystalline supraparticles using an emulsion template and demonstrate that these colloidal supercrystals (SCs) exhibit extended resonant optical behavior resulting in an enhancement in absorption efficiency in the visible range of more than 2 orders of magnitude with respect to the case of dispersed QDs. This successful light trapping strategy is complemented by the enhanced excitonic coupling observed in ligand-exchanged SCs, experimentally demonstrated through ultrafast transient absorption spectroscopy and leading to the formation of a free biexciton system on sub-picosecond time scales. These results introduce a colloidal metamaterial designed by self-assembly from the bottom up, simultaneously featuring a combination of nanoscale and mesoscale properties leading to simultaneous photonic and excitonic coupling, therefore presenting the nanocrystal analogue of supramolecular structures.

Chemo- and Thermomechanically Configurable 3D Optical Metamaterials Constructed from Colloidal Nanocrystal Assemblies

Abstract: Nanofabrication has limited most optical metamaterials to 2D or, often with multiple patterning steps, simple 3D meta-atoms that typically have limited built-in tunability. Here, with a one-step scalable patterning process, we exploit the chemical addressability and structural adaptability of colloidal Au nanocrystal assemblies to transform 2D nanocrystal/Ti bilayers into complex, 3D-structured meta-atoms and to thermally direct their shape morphing and alter their optical properties. By tailoring the length, number, and curvature of 3D helical structures in each meta-atom, we create large-area metamaterials with chiroptical responses of as high as ∼40% transmission difference between left-hand (LCP) and right-hand (RCP) circularly polarized light (ΔT = TRCP – TLCP) that are suitable for broadband circular polarizers and, upon thermally configuring their shape, switch the polarity of polarization rotation. These 3D optical metamaterials provide prototypes for low-cost, large-scale fabrication of optical m...

Favoring the Growth of High-Quality, Three-Dimensional Supercrystals of Nanocrystals

Abstract: A recently developed emulsion-templated assembly method promises the scalable, low-cost, and reproducible fabrication of hierarchical nanocrystal (NC) superstructures. These superstructures derive properties from the unique combination of choices of NC building blocks and superstructure morphology and therefore realize the concept of "artificial solids". To control the final properties of these superstructures, it is essential to control the assembly conditions that yield distinct architectural morphologies. Here, we explore the phase-space of experimental parameters describing the emulsion-templated assembly including temperature, interfacial tension, and NC polydispersity and demonstrate which conditions lead to the growth of the most crystalline NC superstructures or supercrystals. By using a combination of electron microscopy and small-angle X-ray scattering, we show that slower assembly kinetics, softer interfaces, and lower NC polydispersity contribute to the formation of supercrystals with grain sizes up to 600 nm, while reversing these trends yields glassy solids. These results provide a clear path to the realization of higher-quality supercrystals, necessary to many applications.

Nanoparticle diffusion during gelation of tetra poly(ethylene glycol) provides insight into nanoscale structural evolution

Abstract: Single particle tracking (SPT) of PEG grafted nanoparticles (NPs) was used to examine the gelation of tetra poly(ethylene glycol) (TPEG) succinimidyl glutarate (TPEG-SG) and amine (TPEG-A) terminated 4-armed stars. As concentration was decreased from 40 to 20 mg mL−1, the onset of network formation, tgel, determined from rheometry increased from less than 2 to 44 minutes. NP mobility increased as polymer concentration decreased in the sol state, but remained diffusive at times past the tgel determined from rheometry. Once in the gel state, NP mobility decreased, became sub-diffusive, and eventually localized in all concentrations. The NP displacement distributions were investigated to gain insight into the nanoscale environment. In these relatively homogeneous gels, the onset of sub-diffusivity was marked by a rapid increase in dynamic heterogeneity followed by a decrease consistent with a homogeneous network. We propose a gelation mechanism in which clusters initially form a heterogeneous structure which fills in to form a fully gelled relatively homogenous network. This work aims to examine the kinetics of TPEG gelation and the homogeneity of these novel gels on the nanometer scale, which will aid in the implementation of these gels in biomedical or filtration applications.

Nanorod position and orientation in vertical cylinder block copolymer films.

Abstract: The self-assembly of gold nanorods (AuNRs) of different sizes with a block copolymer (BCP) is studied. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films containing P2VP functionalized AuNRs are solvent annealed resulting in a BCP morphology of vertical P2VP cylinders in a PS matrix. At the surface of the PS-b-P2VP films long AuNRs are found in the bridging and vertical states. The bridging state is where the long axis of the AuNR is parallel to the film surface, the AuNR is embedded in the film, and each end of the AuNR is at the top of nearest neighbor P2VP cylinders. The vertical state is where the AuNR is localized within a vertical P2VP cylinder, the AuNR long axis is perpendicular to the film surface and the upper tip of the AuNR is at the film surface. Short AuNRs were found in the bridging and vertical states as well as in a state not observed for the long AuNRs, the centered state. The centered state is where an AuNR has its long axis parallel to the film surface, is embedded in the film, and is centered over a vertical P2VP cylinder. Hybrid particle-field theory (HPFT) simulations modeling the experimental system predict that for the long AuNRs only the bridging state should be observed while for the short AuNRs only the bridging and centered states should be observed. Possible explanations for why the vertical state is observed in experiments despite being thermodynamically unfavorable in simulations are discussed. HPFT simulations also show that when a nanorod is in the bridging state the two cylinders it bridges remain intact and extend from the nanorod to the substrate. Further, the minority block of the BCP is shown to wet the bottom of the bridging nanorod. The bridging state is very promising for the future development of self-assembled nanoscale devices.

Plasmonic Elastic Capsules as Colorimetric Reversible pH‐Microsensors

Abstract: There is a crucial need for effective and easily dispersible colloidal microsensors able to detect local pH changes before irreversible damages caused by demineralization, corrosion, or biofilms occur. One class of such microsensors is based on molecular dyes encapsulated or dispersed either in polymer matrices or in liquid systems exhibiting different colors upon pH variations. They are efficient but often rely on sophisticated and costly syntheses, and present significant risks of leakage and photobleaching damages, which is detrimental for mainstream applications. Another approach consists of exploiting the distance-dependent plasmonic properties of metallic nanoparticles. Still, assembling nanoparticles into dispersible colloidal pH-sensitive sensors remains a challenge. Here, it is shown how to combine optically active plasmonic gold nanoparticles and pH-responsive thin shells into "plasmocapsules." Upon pH change, plasmocapsules swell or shrink. Concomitantly, the distance between the gold nanoparticles embedded in the polymeric matrix varies, resulting in an unambiguous color change. Billions of micron-size sensors can thus be easily fabricated. They are nonintrusive, reusable, and sense local pH changes. Each plasmocapsule is an independent reversible microsensor over a large pH range. Finally, their potential use for the detection of bacterial growth is demonstrated, thus proving that plasmocapsules are a new class of sensing materials.

Engineering the composition of bimetallic nanocrystals to improve hydrodeoxygenation selectivity for 2-acetylfuran

Abstract: Hydrodeoxygenation (HDO) of 2-acetylfuran (2-AF) was examined at 473 K and 33 bar over carbon-supported, bimetallic catalysts. Monodispersed, Pt-based (PtNi, PtCo, and PtCu) and Ni-based (NiCu) nanocrystals (NCs) with well-defined sizes and compositions were prepared via colloidal synthesis. Steady-state, flow-reactor measurements demonstrate that selectivities for HDO reaction to 2-ethylfuran (2-EF) are strongly dependent on the alloy compositions. The HDO of 2-AF is shown to be sequential, where 2-EF can react further to form over-hydrogenated products. The NiCu3/C nanocatalyst was superior to the other bimetallics; with the optimal residence time, it achieved a selectivity of 75 % 2-EF with 80 % conversion of 2-AF, with good stability for up to at least five hours time-on-stream. Deactivation due to coking became an issue when the NCs were deposited on oxide supports with weak acidity (SiO2 and γ-Al2O3). This work provides insights into which bimetallic catalytic systems might be useful for HDO of 2-AF reaction.

Electron accepting naphthalene bisimide ligand architectures for modulation of π-π stacking in nanocrystal hybrid materials.

Abstract: Investigation of charge transfer in quantum dot (QD) systems is an area of great interest. Specifically, the relationship between capping ligand and rate of charge transfer has been studied as a means to optimize these materials. To investigate the role of ligand interaction on the QD surface for electron transfer, we designed and synthesized a series of ligands containing an electron accepting moiety, naphthalene bisimide (NBI). These ligands differ in their steric bulk: as one allows for π-π stacking between the NBI moieties at high surface coverages, while the other does not, allowing for a direct comparison of these effects. Once grafted onto QDs, these hybrid materials were studied using UV-Vis, fluorescence, and transient absorption spectroscopy. Interestingly, the sample with the fastest electron transfer was not the sample with the most NBI π-π stacking, it was instead where these ligands were mixed amongst oleic acid, breaking up H-aggregates between the NBI groups.