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At least 397 records · Page 22

Polyimide-PEG Segmented Block Copolymer Membranes with High Proton Conductivity by Improving Bicontinuous Nanostructure of Ionic Liquid-Doped Films

The structure and properties of segmented block copolymer films of aromatic polyimide (PI) and poly(ethylene glycol) (PEG) doped with an ionic liquid are observed for potential polymer electrolyte membrane applications for fuel cells. Poly(amic acid) precursors of PI-PEG copolymers of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-(1,3-phenylenedioxy) dianiline, and bis(3-aminopropyl) terminated PEG (M n ≈ 1500) are synthesized and then thermally imidized in membrane films, followed by swelling in ethylammonium nitrate (EAN) ionic liquid. The small-angle X-ray scattering results from the EAN-doped PI-PEG copolymer films show disordered bicontinuous phase-separated nanostructures described by Teubner–Strey theory, with the interface fractal dimension determined from the Porod equation. Thermal annealing of the EAN-doped membranes at 100–140 °C results in increased correlation lengths and smoother interfaces of the bicontinuous nanostructures. Such improved nanostructures lead to the increased ionic conductivity by two to five times with the maximum conductivity of 210 mS cm -1 at 60 °C and 70% RH, much greater (nearly fivefold) than that of Nafion films, while maintaining the mechanical stability possibly up to 140 °C. Furthermore, the investigation of the disordered bicontinuous phase-separated nanostructure of EAN-doped PI-PEG copolymer membranes is highly relevant to understanding the nanostructures of hydrated Nafion membranes and segmented block copolymers in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large Photothermal Effect in Sub-40 nm h-BN Nanostructures Patterned Via High-Resolution Ion Beam

The controlled nanoscale patterning of 2D materials is a promising approach for engineering the optoelectronic, thermal, and mechanical properties of these materials to achieve novel functionalities and devices. Herein, high-resolution patterning of hexagonal boron nitride (h-BN) is demonstrated via both helium and neon ion beams and an optimal dosage range for both ions that serve as a baseline for insulating 2D materials is identified. Through this nanofabrication approach, a grating with a 35 nm pitch, individual structure sizes down to 20 nm, and additional nanostructures created by patterning crystal step edges are demonstrated. Raman spectroscopy is used to study the defects induced by the ion beam patterning and is correlated to scanning probe microscopy. Photothermal and scanning near-field optical microscopy measure the resulting near-field absorption and scattering of the nanostructures. These measurements reveal a large photothermal expansion of nanostructured h-BN that is dependent on the height to width aspect ratio of the nanostructures. This effect is attributed to the large anisotropy of the thermal expansion coefficients of h-BN and the nanostructuring implemented. Finally, the photothermal expansion should be present in other van der Waals materials with large anisotropy and can lead to applications such as nanomechanical switches driven by light.

2D materials↗

Nanostructure Imaging Mass Spectrometry: The Role of Fluorocarbons in Metabolite Analysis and Yoctomole Level Sensitivity

Nanostructure Imaging mass spectrometry (NIMS) has become an effective technology for generating ions in the gas phase, providing high sensitivity and imaging capabilities on small molecules, metabolites, drugs, and drug metabolites. Specifically, laser desorption from the nanostructure surfaces results in efficient energy transfer, low background chemical noise, and the nondestructive release of analyte ions into the gas phase. The modification of nanostructured surfaces with fluorous compounds, either covalent or non-covalent, has played an important role in gaining high efficiency/sensitivity by facilitating analyte desorption from the non-adhesive surfaces, and minimizing the amount of laser energy required. In addition, the hydrophobic fluorinated nanostructure surfaces have aided in concentrating deposited samples into fine micrometer sized spots, a feature that further facilitates efficient desorption/ionization. These fluorous nanostructured surfaces have opened up NIMS to very broad applications including enzyme activity assays and imaging, providing low background, efficient energy transfer, nondestructive analyte ion generation, super-hydrophobic surfaces, and ultra-high detection sensitivity

59 BASIC BIOLOGICAL SCIENCES↗

Supramolecular assembly of multifunctional maspin-mimetic nanostructures as a potent peptide-based angiogenesis inhibitor

Aberrant angiogenesis plays a large role in pathologies ranging from tumor growth to macular degeneration. Anti-angiogenic proteins have thus come under scrutiny as versatile, potent therapeutics but face problems with purification and tissue retention. We report here on the synthesis of supramolecular nanostructures that mimic the anti-angiogenic activity of maspin, a class II tumor suppressor protein. These maspin-mimetic nanostructures are formed via self-assembly of small peptide amphiphiles containing the g-helix motif of maspin. Using tubulogenesis assays with human umbilical vein endothelial cells, we demonstrate that maspin-mimetic nanostructures show anti-angiogenic activity at concentrations that are significantly lower than those necessary for the g-helix peptide. Furthermore, in vivo assays in the chick chorioallantoic membrane show maspin-mimetic nanostructures to be effective over controls at inhibiting angiogenesis. Thus, in conclusion, the nanostructures investigated here offer an attractive alternative to the use of anti-angiogenic recombinant proteins in the treatment of cancer or other diseases involving abnormal blood vessel formation.

59 BASIC BIOLOGICAL SCIENCES↗

Covalent functionalization of metal oxide and carbon nanostructures with polyoctasilsesquioxane (POSS) and their incorporation in polymer composites

Polyoctasilsesquioxane (POSS) has been employed to covalently functionalize nanostructures of TiO{sub 2}, ZnO and Fe{sub 2}O{sub 3} as well as carbon nanotubes, nanodiamond and graphene to enable their dispersion in polar solvents. Covalent functionalization of these nanostructures with POSS has been established by electron microscopy, EDAX analysis and infrared spectroscopy. On heating the POSS-functionalized nanostructures, silica-coated nanostructures are obtained. POSS-functionalized nanoparticles of TiO{sub 2}, Fe{sub 2}O{sub 3} and graphite were utilized to prepare polymer-nanostructure composites based on PVA and nylon-6,6.

36 MATERIALS SCIENCE↗

Magnetic field-assisted synthesis of wire-like Co{sub 3}O{sub 4} nanostructures: Electrochemical and photocatalytic studies

Graphical abstract: Schematic illustration for the magnetic field-assisted growth of wire-like Co{sub 3}O{sub 4} nanostructure. Display Omitted Highlights: ► Co{sub 3}O{sub 4} nanowires are prepared by magnetic field hydrothermal reduction and annealing. ► These Co{sub 3}O{sub 4} nanowires possess enhanced capacitance. ► The Co{sub 3}O{sub 4} nanowires have a good photocatalytic activity for methyl orange. -- Abstract: Wire-like Co{sub 3}O{sub 4} nanostructures were prepared by the combination of magnetic field-assisted hydrothermal reduction of cobalt ions and the subsequent ambient annealing at 500 °C. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the structure and morphological evolution of the products. The results show that the wire-like nanostructures possess diameters about 250 nm and lengths over 10 μm. The possible formation mechanism of the wire-like Co{sub 3}O{sub 4} nanostructures is also proposed based on the SEM results. Galvanostatic methods were used to characterize the electrochemical properties. The measurements indicate that the wire-like Co{sub 3}O{sub 4} nanostructures show larger discharge and charge capacities than that of spherical Co{sub 3}O{sub 4} nanoparticles prepared in the absence of magnetic field. In addition, the photocatalytic activity of the products was investigated by measuring the photodegradation of methyl orange solution under ultraviolet radiation, which shows that both the wire-like and spherical products have a good photocatalytic activity.

36 MATERIALS SCIENCE↗

Fabrication of ZnO nanostructures sensitized with CdS quantum dots for photovoltaic application using a convenient solution method

Zinc oxide (ZnO) nanostructures sensitized with cadmium sulfide quantum dots (CdS QDs) were fabricated using a simple and inexpensive solution method. ZnO nanostructures, in the form of either nanocones or nanorods, were first grown directly from fluorine-doped tin oxide (FTO) substrates in aqueous solutions of zinc nitrate (Zn(NO{sub 3}){sub 2}) and hexamethylenetetramine (HMTA, C{sub 6}H{sub 12}N{sub 4}) under external voltages. Then, CdS QDs were attached to these ZnO nanostructures via reactions in the mixed aqueous solutions of cadmium nitrate (Cd(NO{sub 3}){sub 2}) and thioacetamide (C{sub 2}H{sub 5}NS). Photovoltaic responses were obtained from the quantum dot sensitized solar cells (QDSSCs) in which these CdS QD-covered ZnO nanostructures were employed as the photoanodes. The morphologies of the ZnO nanostructures, which could be effectively modulated via the substrate location in the solutions during the fabrication, were found to have played an important role in determining the properties of the QDSSCs.

36 MATERIALS SCIENCE↗

Low-Temperature Hydrothermal Synthesis of Colloidal Crystal Templated Nanostructured Single-Crystalline ZnO

Single crystal semiconductors almost always exhibit better optoelectrical properties than their polycrystalline or amorous counterparts. While three-dimensionally (3D) nanostructured semiconductor devices have been proposed for numerous applications, in the vast majority of reports, the semiconductor is polycrystalline or amorphous, greatly reducing the potential for advanced properties. While technologies for 3D structuring of semiconductors via use of a 3D template have advanced significantly, approaches for epitaxially growing nanostructured single crystal semiconductors within a template remain limited. Here, we demonstrate the epitaxial growth of 3D-structured ZnO through colloidal templates formed from 225 nm and 600 nm diameter colloidal particles via a low-temperature (~80 °C) hydrothermal process using a flow reactor. The effects of the pH of the reaction solution as well as the additive used on the 3D epitaxy process are investigated. The optical and electrical properties of the epitaxially grown nanostructured ZnO are probed by reflectance, photoluminescence, and Hall effect measurements. It is found that the epitaxially grown nanostructured ZnO generally exhibits superior properties than those of polycrystalline ZnO. The demonstrated hydrothermal epitaxy process should be applicable to other chemical solution-based deposition techniques and help extend the range of materials that can be grown into a 3D nanostructured single-crystalline form.

36 MATERIALS SCIENCE↗

Single-Molecule Fluorescence Investigations of Solute Transport Dynamics in Nanostructured Membrane Separation Materials

Many materials used for membrane separations comprise of nanoscale structures such as pores and domains. Such nanostructures often control the solute permeability and selectivity of separation membranes. Thus, for future development of highly efficient separation membranes, it is important to understand the structural and chemical properties of these nanostructures, and also their influences on solute transport dynamics. For the last two decades, single-molecule fluorescence techniques have been used to measure the detailed dynamics of solute molecules diffusing in various nanostructured materials, giving valuable insights into molecular transport mechanisms influenced by nanoscale material heterogeneity. This Perspective will discuss recent single-molecule fluorescence studies on solute diffusion in materials relevant to membrane separations, including dense polymer films and nanoporous materials. These studies have revealed the formation and properties of nanostructures, and unique transport dynamics of solute molecules manipulated by their confinement and partitioning to the nanostructures, which play key roles in membrane separations. Furthermore, this Perspective will also point out scientific challenges toward thorough understanding of molecular-level mechanisms in membrane separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Diversity of Arthropod Biophotonic Nanostructures Spans Amphiphilic Phase-Space

Many organisms, especially arthropods, produce vivid interference colors using diverse mesoscopic (100-350 nm) integumentary biophotonic nanostructures that are increasingly being investigated for technological applications. Despite a century of interest, precise structural knowledge of many biophotonic nanostructures and the mechanisms controlling their development remain tentative, when such knowledge can open novel biomimetic routes to facilely self-assemble tunable, multifunctional materials. Here, we use synchrotron small-angle X-ray scattering and electron microscopy to characterize the photonic nanostructure of 140 integumentary scales and setae from ~127 species of terrestrial arthropods in 85 genera from 5 orders. We report a rich nanostructural diversity, including triply periodic bicontinuous networks, close-packed spheres, inverse columnar, perforated lamellar, and disordered spongelike morphologies, commonly observed as stable phases of amphiphilic surfactants, block copolymer, and lyotropic lipid-water systems. Diverse arthropod lineages appear to have independently evolved to utilize the self-assembly of infolding lipid-bilayer membranes to develop biophotonic nanostructures that span the phase-space of amphiphilic morphologies, but at optical length scales.

Saranathan, Vinod Kumar↗

Self-Assembled One-Dimensional Porphyrin Nanostructures with Enhanced Photocatalytic Hydrogen Generation

There has been a widespread interest in the preparation of self-assembled porphyrin nanostructures and their ordered arrays, aiming to emulate natural light harvesting processes and energy storage and to develop new nanostructured materials for photocatalytic process. In this paper, we report controlled synthesis of one-dimensional porphyrin nanostructures such as nanorods and nanowires with well-defined self-assembled porphyrin networks that enable efficient energy transfer for enhanced photocatalytic activity in hydrogen generation. Preparation of these one-dimensional nanostructures is conducted through noncovalent self-assembly of porphyrins confined within surfactant micelles. X-ray diffraction and transmission electron microscopy results reveal that these one-dimensional nanostructures contain stable single crystalline structures with controlled interplanar separation distance. Optical absorption characterizations show that the self-assembly enables effective optical coupling of porphyrins, resulting in much more enhanced optical absorption in comparison with the original porphyrin monomers, and the absorption bands red shift to more extensive visible light spectrum. Finally, the self-assembled porphyrin network facilitates efficient energy transfer among porphyrin molecules and the delocalization of excited state electrons for enhanced photocatalytic hydrogen production under visible light.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Periodic Arrangement of Lipopolysaccharides Nanostructures Accelerates and Enhances the Maturation Processes of Dendritic Cells

This work reports an important application of nanomaterials consisting of biological ligands, such as lipopolysaccharides (LPS) nanostructures. Upon immobilization onto surfaces as periodic arrays of nanostructures, these surface-bound LPS nanostructures significantly impacted the maturation process of bone marrow derived dendritic cells (BMDCs): accelerating the maturation process in comparison to other means of ligand presentations such as LPS solution and monolayers on surfaces. In some cases, LPS nanostructures led to a new maturation phenotype in vitro characterized by hyper-dendritized morphology. This level of maturation enhancement was observed for the first time in vitro. Possible mechanisms leading to the acceleration and enhancement of BMDC maturation were also discussed. This work demonstrates an important concept: surface-bound nanostructures of ligands provide a new and powerful cue for regulating cellular signaling processes. The fact that primary cells’ signaling processes, such as BMDC maturation, can be altered suggests a new means for programming dendritic cells for immune therapy.

59 BASIC BIOLOGICAL SCIENCES↗

Structure and Magnetism Evolution from FeCo Nanoparticles to Hollow Nanostructure Conversion for Magnetic Applications

Hollow nanostructures have witnessed an increasing interest in emerging fields, including energy storage electrodes, nanocatalysis, photonics, and biomedical carriers, etc. The fundamental mechanisms for hollowing conversion chemistry of complex nanoalloys is indispensable to grow such nanostructures with controlled compositions and functionalities. In this contribution, the Kirkendall effect on magnetic Fe-Co bimetallic alloys with the formation of hollow nanostructures for exchange interactions was studied. The rich diffusion kinetics of binary Fe-Co alloys accompanied with its conversion from solid, core-shell to hollow nanostructures were been captured through X-ray spectroscopy and electron microscopy. We further report the cation exchange improved magnetic performance of hollow nanostructures with increasing the crystallinity.

36 MATERIALS SCIENCE↗

Low-dimensional hyperthin FeS 2 nanostructures for efficient and stable hydrogen evolution electrocatalysis

We report a scalable, solution-processing method for synthesizing low-dimensional hyperthin FeS 2 nanostructures, and we show that 2D FeS 2 disc nanostructures are an efficient and stable hydrogen evolution electrocatalyst. By changing the Fe:S ratio in the precursor solution, we were able to preferentially synthesize either 1D wire or 2D disc nanostructures. The 2D FeS 2 disc structure has the highest electrocatalytic activity for the hydrogen evolution reaction, comparable to platinum in neutral pH conditions. Moreover, the ability of the FeS 2 nanostructures to generate hydrogen was confirmed by scanning electrochemical microscopy, and the 2D disc nanostructures were able to generate hydrogen for over 125 h.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Coarse-Grained Simulations for the Characterization and Optimization of Hybrid Protein–DNA Nanostructures

We present here the combination of experimental and computational modeling tools for the design and characterization of protein–DNA hybrid nanostructures. Our work incorporates several features in the design of these nanostructures: (1) modeling of the protein–DNA linker identity and length; (2) optimizing the design of protein–DNA cages to account for mechanical stresses; (3) probing the incorporation efficiency of protein–DNA conjugates into DNA nanostructures. The modeling tools were experimentally validated using structural characterization methods like cryo-TEM and AFM. Our method can be used for fitting low-resolution electron density maps when structural insights cannot be deciphered from experiments, as well as enable in-silico validation of nanostructured systems before their experimental realization. Finally, these tools will facilitate the design of complex hybrid protein–DNA nanostructures that seamlessly integrate the two different biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗

Halide Anions as Shape-Directing Agents for Obtaining High-Quality Anisotropic Gold Nanostructures

The fundamental role of halide anions in the seed-mediated synthesis of anisotropic noble metal nanostructures has been a subject of debate within the nanomaterials community. Herein, we systematically investigate the roles of chloride, bromide and iodide anions in mediating the growth of anisotropic Au nanostructures. A high-purity surfactant solution of hexadecyltrimethylammonium bromide (CTABr) is used to reliably probe the role of each halide anion without interference from impurities. Our investigation reveals that bromide anions are required for the formation of Au nanorods, while the controlled combination of both bromide and iodide anions are necessary for the production of high-quality Au nanoprisms. Chloride anions, however, are ineffective at promoting anisotropic architectures and are detrimental to nanorod and/or nanoprism growth at high concentrations. We examine the seed structure and propose a growth model based on facet-selective adsorption on low-index Au facets to rationalize the nanostructures obtained by these methods. Our approach provides a facile synthesis of anisotropic Au nanostructures by way of a single growth solution and yields the desired morphologies with high purity. These results demonstrate that appropriate combinations of halide anions provide a versatile paradigm for manipulating the morphological distribution of Au nanostructures.

Environmental Molecular Sciences Laboratory↗

Highly branched cobalt phosphide nanostructures for hydrogen-evolution electrocatalysis

CoP nanostructures that exposed predominantly (111) crystal facets were synthesized and evaluated for performance as electrocatalysts for the hydrogen-evolution reaction (HER). The branched CoP nanostructures were synthesized by reacting cobalt(II) acetylacetonate with trioctylphosphine in the presence of trioctylphosphine oxide. Electrodes comprised of the branched CoP nanostructures deposited at a loading density of ~1 mg cm -2 on Ti electrodes required an overpotential of -117 mV to produce a current density of -20 mA cm -2 in 0.50 M H 2 SO 4 . Hence the branched CoP nanostructures belong to the growing family of highly active non-noble-metal HER electrocatalysts. Finally, comparisons with related CoP systems have provided insights into the impact that shape-controlled nanoparticles and nanoparticle–electrode interactions have on the activity and stability of nanostructured HER electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

When ruthenia met titania: Achieving extraordinary catalytic activity at low temperature by nanostructuring of oxides

Nanostructured RuO x /TiO 2 (110) catalysts have a remarkable catalytic activity for CO oxidation at temperatures in the range of 350–375 K. Furthermore, the RuO 2 (110) surface has no activity. The state-of-the-art DFT calculations indicate that the main reasons for such an impressive improvement in the catalytic activity are: (i) a decrease of the diffusion barrier of adsorbed O atoms by around 40%, from 1.07 eV in RuO 2 (110) to 0.66 eV in RuO x /TiO 2 (110), which explains the shift of the activity to lower temperatures and (ii) a lowering of the barrier by 20% for the association of adsorbed CO and O species to give CO 2 (the main barrier for the CO oxidation reaction) passing from around 0.7 eV in RuO 2 (110) to 0.55 eV in RuO x /TiO 2 (110). We show that the catalytic properties of ruthenia are strongly modified when supported as nanostructures on titania, attaining higher activity at temperatures 100 K lower than that needed for pure ruthenia. As in other systems consisting of ceria nanostructures supported on titania, nanostructured ruthenia shows strongly modified properties compared to the pure oxide, consolidating the fact that the nanostructuring of oxides is a main way to attain higher catalytic activity at lower temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗