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At least 307 records · Page 17

Switching of self-assembly in a peptide nanostructure with a specific enzyme

Peptide self-assembly has been shown to be a useful tool for the preparation of bioactive nanostructures, and recent work has demonstrated their potential as therapies for regenerative medicine. In principle, one route to make these nanostructures more biomimetic would be to incorporate in their molecular design the capacity for biological sensing. We report here on the use of a reversible enzymatic trigger to control the assembly and disassembly of peptide amphiphile (PA) nanostructures. The PA used in these studies contained a consensus substrate sequence specific to protein kinase A (PKA), a biological enzyme important for intracellular signaling that has also been shown to be an extracellular cancer biomarker. Upon treatment with PKA, this PA molecule becomes phosphorylated causing the high aspect-ratio filamentous PA nanostructures to disassemble. Treatment with an enzyme to cleave the phosphate group results in reformation of the filamentous nanostructures. We also show that disassembly in the presence of PKA allows the enzyme-triggered release of an encapsulated cancer drug. In addition, these drug-loaded nanostructures were found to induce preferential cytotoxicity in a cancer cell line that is known to secrete high levels of PKA. This ability to control nanostructure through an enzymatic switch could allow for the preparation of highly sophisticated and biomimetic materials that incorporate a biological sensing capability to enable therapeutic specificity.

59 BASIC BIOLOGICAL SCIENCES↗

Nanostructured cerium oxide: preparation, characterization, and application in energy and environmental catalysis

Nanostructured cerium oxide (CeO 2 ) with outstanding physical and chemical properties has attracted extensive interests over the past few decades in environment and energy-related applications. With controllable synthesis of nanostructured CeO 2 , much more features were technologically brought out from defect chemistry to structure-derived effects. This paper highlights recent progress on the synthesis and characterization of nanostructured ceria-based materials as well as the traditional and new applications. Specifically, several typical applications based on the desired ceria nanostructures are focused to showcase the importance of nanostructure-derived effects. Moreover, some challenges and perspectives on the nanostructured ceria are presented, such as defects controlling and retainment, scale-up fabrication, and monolithic devices. Hopefully, this paper can provide an improved understanding of nanostructured CeO 2 and offer new opportunities to promote the further research and applications in the future.

36 MATERIALS SCIENCE↗

Gallstone-Formation-Inspired Bimetallic Supra-nanostructures for Computed-Tomography-Image-Guided Radiation Therapy

Inspired by the gallstone formation mechanism, we report here a fast one-pot synthesis of high-surface-area bimetallic hierarchical supra-nanostructures. As gallstones are generated from metal cholate complexes, cholate bile acid molecules with Au/Ag metal precursors formed stable nanocomplexes aggregated with metal Au ions and preformed ~2 nm silver halide nanoparticles before reduction. When a reducing agent was added, the metal cholate nanocomplexes quickly formed noble bimetallic hierarchical supra-nanostructures. The morphology of bimetallic supra-nanostructures could be tailored by changing the feeding ratio of each metal precursor. In situ synchrotron small-angle X-ray scattering measurement with a custom-designed reaction cell showed two-step growth and attachment behavior toward hierarchical supra-nanostructures from the gallstone-formation-inspired metal cholate nanocomplexes in a 60 s reaction. Additional wide-angle X-ray scattering, X-ray absorption near-edge structure, in situ Fourier transform infrared, and high-resolution scanning transmission electron microscopy investigations subsequently revealed the mechanism for the evolution of bimetallic hierarchical supra-nanostructures. The gallstone-formation-inspired synthesis mechanism can be universally applied to other metals, for example, Pt–Ag and Pd–Ag bimetallic nanostructures. The synthesized high-surface-area bimetallic supra-nanostructures demonstrated significantly enhanced X-ray computed tomography imaging contrast and radiosensitizing effect for a potential image-guided nanomedicine application. We believe that our synthetic method inspired by gallstone formation and understanding represents an important step toward the development of hierarchical nanoparticles for various applications.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Nano-array integrated monolithic devices: toward rational materials design and multi-functional performance by scalable nanostructures assembly

We report the scalable three-dimensional (3-D) integration of functional nanostructures into applicable platforms represents a promising technology to meet the ever-increasing demands of fabricating high performance devices featuring cost-effectiveness, structural sophistication and multi-functional enabling. Such an integration process generally involves a diverse array of nanostructural entities (nano-entities) consisting of dissimilar nanoscale building blocks such as nanoparticles, nanowires, and nanofilms made of metals, ceramics, or polymers. Various synthetic strategies and integration methods have enabled the successful assembly of both structurally and functionally tailored nano-arrays into a unique class of monolithic devices. The performance of nano-array based monolithic devices is dictated by a few important factors such as materials substrate selection, nanostructure composition and nano-architecture geometry. Therefore, the rational material selection and nano-entity manipulation during the nano-array integration process, aiming to exploit the advantageous characteristics of nanostructures and their ensembles, are critical steps towards bridging the design of nanostructure integrated monolithic devices with various practical applications. In this article, we highlight the latest research progress of the two-dimensional (2-D) and 3-D metal and metal oxide based nanostructural integrations into prototype devices applicable with ultrahigh efficiency, good robustness and improved functionality. Lastly, selective examples of nano-array integration, scalable nanomanufacturing and representative monolithic devices such as catalytic converters, sensors and batteries will be utilized as the connecting dots to display a roadmap from hierarchical nanostructural assembly to practical nanotechnology implications ranging from energy, environmental, to chemical and biotechnology areas.

36 MATERIALS SCIENCE↗

A four-probe thermal transport measurement method for nanostructures

Several experimental techniques reported in recent years have enabled the measurement of thermal transport properties of nanostructures. However, eliminating the contact thermal resistance error from the measurement results has remained a critical challenge. Here, we report a different four-probe measurement method that can separately obtain both the intrinsic thermal conductance and the contact thermal resistance of individual nanostructures. The measurement device consists of four microfabricated, suspended metal lines that act as resistive heaters and thermometers, across which the nanostructure sample is assembled. The method takes advantage of the variation in the heat flow along the suspended nanostructure and across its contacts to the four suspended heater and thermometer lines, and uses sixteen sets of temperature and heat flow measurements to obtain nine of the thermal resistances in the measurement device and the nanostructure sample, including the intrinsic thermal resistance and the two contact thermal resistances to the middle suspended segment of the nanostructure. Two single crystalline Si nanowires with different cross sections are measured in this work to demonstrate the effectiveness of the method. This four-probe thermal transport measurement method can lead to future discoveries of unique size-dependent thermal transport phenomena in nanostructures and low-dimensional materials, in addition to providing reliable experimental data for calibrating theoretical models.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Review—Electrolytic Metal Atoms Enabled Manufacturing of Nanostructured Sensor Electrodes

Sensing materials play a key role in the successful implementation of electrochemical sensors, and nanotechnology has emerged as an important and rapidly growing field for stimulating the innovation of high-performance sensors. The fabrication, characterization, and evaluation of the nanostructured electrodes are therefore a focus of this field. Compared to a variety of dry and wet technologies which have been extensively developed for this purpose, electrochemical methods are typically convenient, highly effective, and potentially low-cost for the production of different nanostructures. This minireview is designed to introduce a unique electrochemical method - electrolytic metal-atom enabled manufacturing (EM 2 ) and its application in electrochemical sensors. The EM 2 technique employs electrolytic metal atoms generated from their corresponding salt precursor as a tool to nanostructure a wide range of substrate electrodes used in electrochemical sensors, based on a one-pot electrochemical deposition and dissolution of the metal atoms in the same electrolyte bath. Briefly, the metal atoms are electrodeposited on a substrate electrode during the cathode reduction, and they are selectively removed from the substrate during the subsequent anode oxidation. Because of the interactions between the electrolytic metal atoms and the substrate atoms, the repetitive electrodeposition and dissolution of the former on the substrate enable the nanostructuration of the substrate, particularly within its surface layers. The nanostructured electrodes have demonstrated very attractive performance for the determination of numerous analytes, such as high sensitivity and selectivity, high interference tolerance, and low detection limits. However, the EM 2 technique and the application of the resulting nanostructured electrodes in electrochemical sensors and beyond have still been very limitedly investigated. In order to bring the community from academic, industries, agencies, and customers together to develop the EM 2 technique and advance electrochemical sensor systems, this minireview will introduce the thermodynamic and kinetic fundamentals of this technique, the characterization of resulting nanostructures, the analysis of their electrochemical behavior, and the implementation of this technique for the development of advanced sensor electrodes. Finally, an outlook with a focus on further research areas is provided.

Jiang, Junhua (ORCID:0000000324379812)↗

The Development of Metal Oxide Chemical Sensing Nanostructures

This paper discusses sensor development based on metal oxide nanostructures and microsystems technology. While nanostructures such as nanowires show significant potential as enabling materials for chemical sensors, a number of significant technical challenges remain. This paper discusses development to address each of these technical barriers: 1) Improved contact and integration of the nanostructured materials with microsystems in a sensor structure; 2) Control of nanostructure crystallinity to allow control of the detection mechanism; and 3) Widening the range of gases that can be detected by fabricating multiple nanostructured materials. A sensor structure composed of three nanostructured oxides aligned on a single microsensor has been fabricated and tested. Results of this testing are discussed and future development approaches are suggested. It is concluded that while this work lays the foundation for further development, these are the beginning steps towards realization of repeatable, controlled sensor systems using oxide based nanostructures.

Hunter, G. W.↗

Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing

The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.

Guo, Junpeng↗

Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing

The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.

Guo, Junpeng↗

Controlled placement and orientation of nanostructures

A method for controlled deposition and orientation of molecular sized nanoelectromechanical systems (NEMS) on substrates is disclosed. The method comprised: forming a thin layer of polymer coating on a substrate; exposing a selected portion of the thin layer of polymer to alter a selected portion of the thin layer of polymer; forming a suspension of nanostructures in a solvent, wherein the solvent suspends the nanostructures and activates the nanostructures in the solvent for deposition; and flowing a suspension of nanostructures across the layer of polymer in a flow direction; thereby: depositing a nanostructure in the suspension of nanostructures only to the selected portion of the thin layer of polymer coating on the substrate to form a deposited nanostructure oriented in the flow direction. By selectively employing portions of the method above, complex NEMS may be built of simpler NEMSs components.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Surface doping of nanostructures

This disclosure provides systems, methods, and apparatus related to surface doping of nanostructures. In one aspect a plurality of nanostructures is fabricated with a solution-based process using a solvent. The plurality of nanostructures comprises a semiconductor. Each of the plurality of nanostructures has a surface with capping species attached to the surface. The plurality of nanostructures is mixed in the solvent with a dopant compound that includes doping species. During the mixing the capping species on the surfaces of the plurality of nanostructures are replaced by the doping species. Charge carriers are transferred between the doping species and the plurality of nanostructures.

Sahu, Ayaskanta↗

Electrothermal coating with nanostructures mixture and method for making the same

An electrothermal coating can include a nanostructure mixture randomly dispersed in a polymer matrix with more than one type of low-dimensional nanostructure. These types of low-dimensional nanostructures can include a combination of a nanospheroid plus one or both of a linear nanostructure and a planar nanostructure. Useful conductivity is achieved, while concentration of the mixed nanostructures is within the cured polymer composite coating being below the percolation limit of each individual carbon nanostructure type, alone, within an identical polymer matrix.

36 MATERIALS SCIENCE↗

Recent progress in nanostructured multiferroic Bi{sub 2}FeCrO{sub 6} thin films

We report the latest progress on the growth and characterization of Bi{sub 2}FeCrO{sub 6} (BFCO), a recently discovered multiferroic system. BFCO thin films and nanostructures exhibit exceptional multiferroic properties at room temperature. The growth of pure BFCO thin films on STO substrates is possible only in a narrow window of deposition parameters (i.e., Oxygen pressure pO{sub 2}=1.2 Multiplication-Sign 10{sup -2} mbar and around a substrate temperature T{sub S}=680 Degree-Sign C). The epitaxial growth stabilizes the metastable single phase of this material and promotes the Fe/Cr cation ordering in both thin films and nanostructures. This cationic ordering which is responsible for good magnetic properties of BFCO is also at the origin of pronounced photovoltaic (PV) properties observed in the epitaxial films grown on STO substrates. The results indicate that the ferroelectric polarization plays a dominant role in the observed PV effect. - Graphical abstract: (Top) Crystal structure of BFCO thin films deposited on (1 1 1)-oriented SrTiO3:Nb substrates and direct evidence of the presence of cationic ordering Fe/Cr in the films. (Bottom) Control of the crystal orientation and the shape of the epitaxial nanostructures by the orientation of the niobium-doped STO substrates. Highlights: Black-Right-Pointing-Pointer Growth optimization of Bi{sub 2}FeCrO{sub 6} (BFCO) thin films and nanostructures by pulsed laser deposition. Black-Right-Pointing-Pointer Ordered BFCO single phase have been stabilized by epitaxial strain. Black-Right-Pointing-Pointer Arbitrary patterns of heteroepitaxial multiferroic BFCO nanostructures have been fabricated by PLD combined with nanostenciling. Black-Right-Pointing-Pointer Experimental characterizations revealed the excellent multiferroic character of BFCO thin films and nanostructures. Black-Right-Pointing-Pointer Unprecedentedly high power conversion efficiency for ferroelectrics was observed in 125 nm-thick highly ordered BFCO films.Graphical abstract legend.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionic liquids-modulated two-phase thermal synthesis of three-dimensional CuS nanostructures

A novel method was proposed for successful fabrication of CuS nanostructures with various morphologies. At the ionic liquids (ILs)-modulated CHCl{sub 3}-H{sub 2}O interface, copper cupferronate [Cu(cup){sub 2}] in CHCl{sub 3} reacted with thiourea in water to generate CuS nanostructures via a solvothermal reaction process. The effects of alkyl chain length of imidazolium cations and nature of anions of the ILs, molar ratio of Cu(cup){sub 2} to thiourea, the reaction temperature and time on the morphology of the products were studied systematically. It was shown that by changing alkyl chain length of imidazolium cations and nature of anions of the ILs, CuS nanostructures with various morphologies, including flowers, urchins, large nanodisks and nanoparticles, could be obtained at the liquid-liquid interface, and the ILs played important template roles in directing the formation of CuS nanostructures. Furthermore, the as-prepared CuS samples exhibited high catalytic activity for photodegradation of methyl orange and thermal decomposition of ammonium perchlorate. - Graphical abstract: At the ionic liquids-modulated CHCl{sub 3}-H{sub 2}O interface, the CuS nanostructures with the various morphologies of flowers, urchins, large nanodisks and nanoparticles have been successfully prepared via a solvothermal reaction process. Highlights: Black-Right-Pointing-Pointer The properties of oil-H{sub 2}O interface can be modulated by employing different ILs. Black-Right-Pointing-Pointer The modulated interface has been used to prepare CuS nanostructures with various morphologies. Black-Right-Pointing-Pointer The CuS samples exhibited high catalytic activity for the photodegradation of methyl orange.

36 MATERIALS SCIENCE↗

Coherent 3D nanostructure of γ-Al{sub 2}O{sub 3}: Simulation of whole X-ray powder diffraction pattern

The structure and nanostructure features of nanocrystalline γ-Al{sub 2}O{sub 3} obtained by dehydration of boehmite with anisotropic platelet-shaped particles were investigated. The original models of 3D coherent nanostructure of γ-Al{sub 2}O{sub 3} were constructed. The models of nanostructured γ-Al{sub 2}O{sub 3} particles were first confirmed by a direct simulation of powder X–Ray diffraction (XRD) patterns using the Debye Scattering Equation (DSE) with assistance of high-resolution transmission electron microscopy (HRTEM) study. The average crystal structure of γ-Al{sub 2}O{sub 3} was shown to be tetragonally distorted. The experimental results revealed that thin γ-Al{sub 2}O{sub 3} platelets were heterogeneous on a nanometer scale and nanometer-sized building blocks were separated by partially coherent interfaces. The XRD simulation results showed that a specific packing of the primary crystalline blocks in the nanostructured γ-Al{sub 2}O{sub 3} particles with formation of planar defects on (001), (100), and (101) planes nicely accounted for pronounced diffuse scattering, anisotropic peak broadening and peak shifts in the experimental XRD pattern. The identified planar defects in cation sublattice seem to be described as filling cation non-spinel sites in existing crystallographic models of γ-Al{sub 2}O{sub 3} structure. The overall findings provided an insight into the complex nanostructure, which is intrinsic to the metastable γ-Al{sub 2}O{sub 3} oxide. - Highlights: • Thin plate-like crystallites of γ-Al{sub 2}O{sub 3} were obtained. • Models of 3D coherent nanostructure of γ-Al{sub 2}O{sub 3} were constructed. • Models were verified by simulating XRD patterns using the Debye Scattering Equation. • Specific broadening of XRD peaks was explained in terms of planar defects. • Primary crystalline blocks in γ-Al{sub 2}O{sub 3} are separated by partially coherent interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent advances in MoS{sub 2} nanostructured materials for energy and environmental applications – A review

Molybdenum disulfide (MoS{sub 2}), a layered transition metal dichalcogenide with an analogous structure to graphene, has attracted enormous attention worldwide owing to its use in a variety of applications such as energy storage, energy conversion, environmental remediation and sensors. MoS{sub 2} and graphene have almost similar functional properties such as high charge carrier transport, high wear resistance and good mechanical strength and friction. However, MoS{sub 2} is advantageous over graphene due to its low-cost, abundancy, tailorable morphologies and tuneable band gap with good visible light absorption properties. In this review, we have focussed mainly on recent advances in MoS{sub 2} nanostructured materials for the applications in the broad area of energy and environment. Special attention has been paid to their applications in dye-sensitized solar cells, supercapacitor, Li-ion battery, hydrogen evolution reaction, photocatalysis for the degradation of organic pollutants, chemical/bio sensors and gas sensors. Finally, the challenges to design MoS{sub 2} nanostructures suitable for energy and environmental applications are also highlighted. - Highlights: • Applications of MoS{sub 2} nanostructures towards energy, environmental remediation and sensors were summarized. • Recent advances in the development of MoS{sub 2} nanostructured materials were systematically investigated. • Wide range of energy applications including DSSCs, supercapacitors, Li-ion batteries and HER were reviewed. • Key challenges and optimization of structure for superior performance associated with MoS{sub 2} nanostructures were discussed. • Advances of environmental remediation based on MoS{sub 2} nanostructures were significantly highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile synthesis of mesoporous core-shell TiO{sub 2} nanostructures from TiCl{sub 3}

Highlights: {yields} Stable TiCl{sub 3} solution is adopted as Ti sources. {yields} Low-cost glucose assisted facile solvothermal reactions. {yields} Exquisite core-shell morphology and mesoporous structure of TiO{sub 2} nanostructures. {yields} Superior photocatalytic activity of TiO{sub 2} nanostructures in UV light irradiation. -- Abstract: The present study reports the synthesis and formation process of mesoporous core-shell TiO{sub 2} nanostructures by employing a glucose-assisted solvothermal process using water-ethanol mixture as solvent and subsequent calcination process at 550 {sup o}C for 4 h. X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption analysis were used to investigate the structural properties of these nanostructures. By optimizing the preparation conditions, especially the contents of water and ethanol in the mixture solvent, mesoporous core-shell TiO{sub 2} nanostructures were obtained. These mesoporous nanostructures have anatase phase and exhibit the superior photocatalytic activity. This synthesis route is facile due to the usage of stable and low-cost Ti precursor such as TiCl{sub 3} and is thus applicable for large-scale production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent directed fabrication of Bi{sub 2}WO{sub 6} nanostructures with different morphologies: Synthesis and their shape-dependent photocatalytic properties

Graphical abstract: The morphologies of the Bi{sub 2}WO{sub 6} nanostructures can be easily tuned by altering the solvent composition during the reaction, which will yield flower-like, pancake-like and tubular nanostructures, respectively. Highlights: ► The morphologies of Bi{sub 2}WO{sub 6} can be controlled by tuning the solvent composition. ► The effects of solvent on the morphologies of Bi{sub 2}WO{sub 6} were carefully investigated. ► The growth mechanisms for the as-prepared samples were investigated. ► The morphologies of the samples greatly affect their photocatalytic activities. -- Abstract: In this work, Bi{sub 2}WO{sub 6} with complex morphologies, namely, flower-like, pancake-like, and tubular shapes have been controllably synthesized by a facile solvothermal process. The as-obtained samples are systematically investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The effects of solvents on the morphologies of Bi{sub 2}WO{sub 6} nanostructures are systematically investigated. According to the time-dependent experiments, a two-step growth mode basing on Ostwald ripening process and self-assembly has been proposed for the formation of the flower-like and pancake-like Bi{sub 2}WO{sub 6} nanostructures. The photocatalytic properties of Bi{sub 2}WO{sub 6} nanostructures are strongly dependent on their shapes, sizes, and structures for the degradation of rhodamine B (RhB) under visible-light irradiation. The deduced reasons for the differences in the photocatalytic activities of these Bi{sub 2}WO{sub 6} nanostructures are further discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗