Morphological Growth and Theoretical Understanding of Gold and Other Noble Metal Nanoplates.

For the last decades, the chemical reduction of Au3+ to Au0 has been widely employed to produce various gold nanostructures. In comparison with the fast reduction, the slow reduction is systematically investigated in this research to provide more insights to reveal intermediary process and further disclose the underlying mechanism for growing gold nanostructures by using a series of simple ligands with aldehyde groups as weak reducing agents. The different binding energies of ligands to Aun+ (n=3, 1 and 0) exhibit variable binding affinities in starting, intermediate, and final gold species. For example, formic acid has much stronger binding affinity to Au+ than Au3+ , and thus Au+ intermediate is able to be stabilized/captured during slow reduction of Au3+ . Upon the disproportionation of Au+ to Au0 and Au3+ , formic acid has much stronger binding affinity to the newly formed Au0 than other ligands for the controlled formation of gold nanostructures. Meanwhile, the adsorption of ligands causes substantially decreased surface energies on different gold planes. There are much higher energies on {110} planes compared to the other two {111} and {100} planes with certain ratios in these energies, leading to morphological growth of gold nanosheets. In this paper, we experimentally demonstrate anisotropic growth of gold nanosheets by using various ligands with weak reducing and appropriate coordination capabilities, and further provide insights to understand their morphological growth mechanism behind. This synthetic strategy is successfully extended to prepare silver, palladium, and platinum nanoplates.

Anisotropically branched metal nanostructures.

Metal nanostructures display a multitude of technologically useful properties that can be tailored through fine-tuning of certain parameters, such as size, shape and composition. In many cases, the shape or morphology of metal nanostructures plays the most crucial role in the determination of their properties and their suitability in specific applications. In this tutorial review, we provide a summary of recent research that centers on metal nanostructures having anisotropically branched morphologies. The branched structural features that are exhibited by these materials endow them with unique properties that can be utilized in many important applications. The formation of branched architectures can be achieved in solution through a variety of synthetic strategies, four of which are highlighted in this review and these are: (1) seedless growth, (2) seeded growth, (3) templated growth, and (4) chemical etching. The usefulness of these anisotropically branched metal nanostructures in the areas of plasmonics, catalysis and biomedicine is also presented.

Protein Induces Layer-by-Layer Exfoliation of Transition Metal Dichalcogenides.

Here, we report a general and facile method for effective layer-by-layer exfoliation of transition metal dichalcogenides (TMDs) and graphite in water by using protein, bovine serum albumin (BSA) to produce single-layer nanosheets, which cannot be achieved using other commonly used bio- and synthetic polymers. Besides serving as an effective exfoliating agent, BSA can also function as a strong stabilizing agent against reaggregation of single-layer nanosheets for greatly improving their biocompatibility in biomedical applications. With significantly increased surface area, single-layer MoS2 nanosheets also exhibit a much higher binding capacity to pesticides and a much larger specific capacitance. The protein exfoliation process is carefully investigated with various control experiments and density functional theory simulations. It is interesting to find that the nonpolar groups of protein can firmly bind to TMD layers or graphene to expose polar groups in water, facilitating the effective exfoliation of single-layer nanosheets in aqueous solution. The present work will enable to optimize the fabrication of various 2D materials at high yield and large scale, and bring more opportunities to investigate the unique properties of 2D materials and exploit their novel applications.

Self-assembly of colloidal one-dimensional nanocrystals.

The ability of nanoscopic materials to self-organize into large-scale assembly structures that exhibit unique collective properties has opened up new and exciting opportunities in the field of nanotechnology. Although earlier work on nanoscale self-assembly has focused on colloidal spherical nanocrystals as building blocks, there has been significant interest in recent years in the self-assembly of colloidal nanocrystals having well-defined facets or anisotropic shapes. In this review, particular attention is drawn to anisotropic one-dimensional (1D) nanocrystals, notably nanorods and nanowires, which can be arranged into a multitude of higher-order assembly structures. Different strategies have been developed to realize self-assembly of colloidal 1D nanocrystals and these are highlighted in the first part of this review. Self-assembly can take place (1) on substrates through evaporation control, external field facilitation and template use; (2) at interfaces, such as the liquid-liquid and the gas-liquid interface; and (3) in solutions via chemical bonding, depletion attraction forces and linker-mediated interactions. The choice of a self-assembly approach is pivotal to achieving the desired assembly configuration with properties that can be exploited for functional device applications. In the subsequent sections, the various assembly structures that have been created through 1D nanocrystal self-assembly are presented. These organized structures are broadly categorized into non-close-packed and close-packed configurations, and are further classified based on the different types of 1D nanocrystal alignment (side-by-side and end-to-end), orientation (horizontal and vertical) and ordering (nematic and smectic), and depending on the dimensionality of the structure (2D and 3D). The conditions under which different types of arrangements are achieved are also discussed.

Investigating the multiple roles of polyvinylpyrrolidone for a general methodology of oxide encapsulation.

Growing oxide shells on seed nanoparticles requires the control of several processes: (a) the nucleation and growth of the shell material; (b) the "wetting" of the shell material on the seeds; and (c) the aggregation of the nanoparticles. These processes are influenced by a number of factors, many of which are related. Without understanding the interdependence of these contributing factors, it is difficult to circumvent problems and achieve rational synthesis. We first did a case study on encapsulating Au nanoparticles with ZnO to understand the multiple roles of polyvinylpyrrolidone (PVP) and their dependence on other factors. We developed a general method for coating ZnO on a variety of seeds, including metals, oxides, polymer nanoparticles, graphene oxide, and carbon nanotube. This method can be further extended to include Fe3O4, MnO, Co2O3, TiO2, Eu2O3, Tb2O3, Gd2O3, ß-Ni(OH)2, ZnS, and CdS as the shell materials. The understanding obtained in this systematic study will aid rational design and synthesis of other core-shell nanostructures.

Risk analysis of depression among adult patients with epilepsy of different sex: a retrospective single-center study from China.

Objective: To determine sex differences in the prevalence of depression and assess the risk factors for depression among adult patients with epilepsy from the Dali area of China. Methods: We retrospectively analyzed the clinical data of adult patients with epilepsy who visited the First Affiliated Hospital of Dali University from January 2017 to January 2022. Patient Health Questionnaire-9 was used to assess depressive symptoms in patients with epilepsy. The risk factors of depression were analyzed by binary logistic regression among different sex in patients with epilepsy. Results: There were significant sex differences in depression in patients with epilepsy (p < 0.001), and females were 4.27 times more likely to suffer from depression than males (95% confidence interval: 3.70-4.92). The risk factors for depression among female patients with epilepsy included occupation (p < 0.001), years with epilepsy (p < 0.001), seizure frequency (p < 0.001), seizure type (p < 0.001), etiology (p < 0.001), number of antiseizure medications used (p < 0.001), antiseizure medications (p < 0.001), and electroencephalogram findings (p < 0.001). The risk factors for depression among male patients with epilepsy included age (p < 0.001), ethnicity (p < 0.001), occupation (p < 0.001), years with epilepsy (p < 0.001), seizure frequency (p < 0.001), seizure type (p < 0.001), etiology (p < 0.001), number of antiseizure medications used (p < 0.001), antiseizure medications (p < 0.001), and electroencephalogram findings (p < 0.001). Conclusion: Adult female patients with epilepsy had a higher risk of depression than adult male patients with epilepsy. There were sex differences in the risk factors associated with depression among patients with epilepsy.

Disproportionation for growing copper nanowires and their controlled self-assembly facilitated by ligand exchange.

The coating makes the wire bundle: High-quality free-standing copper nanowires have been successfully produced by disproportionation of Cu(+) in oleylamine. This provides an effective way to prepare high-quality copper nanowires, but also enriches synthetic routes to other nanostructures. These copper nanowires can self-assemble by surface ligand exchange of oleylamine with trioctylphosphine.

Ternary cobalt-iron phosphide nanocrystals with controlled compositions, properties, and morphologies from nanorods and nanorice to split nanostructures.

Structural phase-controlled formation of binary Co(2)P and CoP nanocrystals is achieved by reacting cobalt(II) oleate with trioctylphosphine. In the absence of oleylamine, Co(2)P nanowires are formed at both 290 and 320 °C. In the presence of oleylamine, Co(2)P nanorods are formed at 290 °C, and CoP nanorods are formed at 320 °C. With the simultaneous reaction of iron(III) oleate and cobalt(II) oleate with trioctylphosphine in the presence of oleylamine, ternary Co(2)P-type cobalt-iron phosphide nanostructures are produced at both 290 and 320 °C, corresponding to rice-shaped Co(1.5)Fe(0.5)P nanorods and split Co(1.7)Fe(0.3)P nanostructures, respectively. The controlled incorporation of iron into cobalt phosphide can alter the magnetic properties from paramagnetic binary Co(2)P to ferromagnetic Co(2)P-type ternary cobalt-iron phosphide nanostructures. Meanwhile, the time-dependent morphological evolution from small nanodots/nanorods, through seeded growth to unique split nanostructures is demonstrated in one-pot reaction at 320 °C.

Morphological tuning, self-assembly and optical properties of indium oxide nanocrystals.

In this paper, weak acids, weak bases or their mixtures were used as reaction media/coordinating ligands to achieve systematic morphological control over amphoteric indium oxide nanostructures. Different indium/oleic acid molar ratios from 1 : 0, 1 : 1, 1 : 2, 1 : 3, 1 : 6 and 1 : 15 in non-coordinating, weakly coordinating, strongly coordinating and their mixed media were adopted to prepare irregular aggregated nanoparticles and uniform regular/truncated octahedra, etc. In addition to their strong size-dependent absorption, single-crystalline indium oxide octahedra also gave a strong band-edge emission while irregular indium oxide aggregated nanoparticles only exhibited a weak deep-trap emission. Meanwhile, the truncated octahedra were self-assembled into either zigzag lines or pentagram patterns, and the regular octahedra and truncated cubes were self-assembled into hexagonally packed nanocrystal arrays. In addition, the formation mechanism of the various nanostructures under different conditions was investigated in detail.

[Comparison of the two magnetic resonance deartifact techniques in imaging of different porcelain-fused-to-metal crowns].

OBJECTIVE: This study aimed to compare the porcelain-fused-to-metal (PFM) crown artifact in the magnetic resonance imaging (MRI) of the two magnetic resonance deartifact techniques in studying the application value of the propeller-fast spin-echo T2-weighted sequence (FSE T2WI) in troubleshooting PFM crown artifacts. METHODS: A total of 48 patients with right mandible first molar crown who underwent MRI head examination were chosen as subjects in the study. According to different metal substrates, PFM crowns were divided to three types, namely, nickel-chromium alloy crown, cobalt-chromium alloy crown and titanium crown. The patients received two MRI scan sequences, that is, FSE T2WI and propeller-FSE T2WI sequences. The MRI artifacts areas in two sequences were measured. RESULTS: The difference between FSE T2WI and propeller-FSE T2WI sequences in three kinds of PFM crown was significant (P<0.05). CONCLUSIONS: Propeller-FSE T2WI sequence technique can effectively reduce the metal artifacts of various PFM crowns.

An experimental and theoretical investigation of the anisotropic branching in gold nanocrosses.

In this work, copper (Cu) species were used as reducing reagents in the colloidal preparation of novel cross-shaped gold (Au) nanostructures in oleylamine. The reduction rate can be controlled through an appropriate choice of Cu species to obtain Au nanocrosses of varying sizes. It was found that the presence of Cu species during the nucleation stage is crucial to the formation of a branched morphology. Further analysis revealed that the four primary branches of the Au nanocrosses grow along the <110> and <001> directions, and that secondary branched growth occurs along the <111> direction. First-principles calculations and phase-field models were used to rationalize the observed preferential branching and understand the morphological evolution of the nanocrosses. These unique cross-like Au nanostructures exhibit strong NIR absorption and remarkable plasmonic properties that make them promising materials for optical and biomedical applications.

Rapid Copper Metallization of Textile Materials: a Controlled Two-Step Route to Achieve User-Defined Patterns under Ambient Conditions.

Throughout history earth-abundant copper has been incorporated into textiles and it still caters to various needs in modern society. In this paper, we present a two-step copper metallization strategy to realize sequentially nondiffusive copper(II) patterning and rapid copper deposition on various textile materials, including cotton, polyester, nylon, and their mixtures. A new, cost-effective formulation is designed to minimize the copper pattern migration on textiles and to achieve user-defined copper patterns. The metallized copper is found to be very adhesive and stable against washing and oxidation. Furthermore, the copper-metallized textile exhibits excellent electrical conductivity that is ~3 times better than that of stainless steel and also inhibits the growth of bacteria effectively. This new copper metallization approach holds great promise as a commercially viable method to metallize an insulating textile, opening up research avenues for wearable electronics and functional garments.

Fabrication of bimetallic Cu/Au nanotubes and their sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu(+)-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au(3+) at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Destabilization of gold clusters for controlled nanosynthesis: from clusters to polyhedra.

A precisely controlled destabilization of gold thiolate clusters is demonstrated to grow 12 {110}-faceted gold dodecahedra with greatly enhanced catalytic capability, and reveal the growth mechanism by DFT simulations. This greatly advances our understanding of nanocrystal growth and opens a new window for controlling the dissociation of clusters to produce nanocrystals with specific shapes.

Aqueous route to facile, efficient and functional silica coating of metal nanoparticles at room temperature.

Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields.

Convenient purification of gold clusters by co-precipitation for improved sensing of hydrogen peroxide, mercury ions and pesticides.

An effective separation process is developed to remove free protein from the protein-protected gold clusters via co-precipitation with zinc hydroxide on their surface. After dialysis, the purified clusters exhibit an enhanced fluorescence for improved sensitive detection and selective visualization.

Aqueous synthesis of highly luminescent AgInS2-ZnS quantum dots and their biological applications.

Highly emissive and air-stable AgInS2-ZnS quantum dots (ZAIS QDs) with quantum yields of up to 20% have been successfully synthesized directly in aqueous media in the presence of polyacrylic acid (PAA) and mercaptoacetic acid (MAA) as stabilizing and reactivity-controlling agents. The as-prepared water-dispersible ZAIS QDs are around 3 nm in size, possess the tetragonal chalcopyrite crystal structure, and exhibit long fluorescence lifetimes (>100 ns). In addition, these ZAIS QDs are found to exhibit excellent optical and colloidal stability in physiologically relevant pH values as well as very low cytotoxicity, which render them particularly suitable for biological applications. Their potential use in biological labelling of baculoviral vectors is demonstrated.

Temperature and chemical bonding-directed self-assembly of cobalt phosphide nanowires in reaction solutions into vertical and horizontal alignments.

The preparation of vertically or horizontally aligned self-assemblies of CoP nanowires is demonstrated for the first time by aging them in the reaction solution for a sufficient time at 20 or 0 °C. This strategy opens up a way for exploring the controlled self-assembly of various highly anisotropic nanostructures into long-range ordered structures with collective properties.

Janus Au-TiO2 photocatalysts with strong localization of plasmonic near-fields for efficient visible-light hydrogen generation.

The first use of non-centrosymmetric Janus Au-TiO(2) photocatalysts in efficient, plasmon-enhanced visible-light hydrogen generation is demonstrated. The intense localization of plasmonic near-fields close to the Au-TiO(2) interface, coupled with optical transitions involving localized electronic states in amorphous TiO(2) brings about enhanced optical absorption and the generation of electron-hole pairs for photocatalysis.