Exploiting Organometallic Chemistry to Functionalize Small Cuprous Oxide Colloidal Nanocrystals.

The ligand chemistry of colloidal semiconductor nanocrystals mediates their solubility, band gap, and surface facets. Here, selective organometallic chemistry is used to prepare small, colloidal cuprous oxide nanocrystals and to control their surface chemistry by decorating them with metal complexes. The strategy is demonstrated using small (3-6 nm) cuprous oxide (CuO) colloidal nanocrystals (NC), soluble in organic solvents.

Wet spinning imogolite nanotube fibres: an process study.

Imogolite nanotubes (INTs) form transparent aqueous liquid-crystalline solutions, with strong birefringence and X-ray scattering power. They provide an ideal model system for studying the assembly of one-dimensional nanomaterials into fibres, as well as offering interesting properties in their own right. Here, polarised optical microscopy is used to study the wet spinning of pure INTs into fibres, illustrating the influence of process variables during extrusion, coagulation, washing and drying on both structure and mechanical properties.

Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide.

This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo-copper precursor, mesitylcopper(I) [CuMes] (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu O or Cu S nanoparticles. Use of sub-stoichiometric quantities of protonated ligand (pro-ligand; 0.

Platinum deposition on functionalised graphene for corrosion resistant oxygen reduction electrodes.

Graphene-related materials are promising supports for electrocatalysts due to their stability and high surface area. Their innate surface chemistries can be controlled and tuned functionalisation to improve the stability of both the carbon support and the metal catalyst. Functionalised graphenes were prepared using either aryl diazonium functionalisation or non-destructive chemical reduction, to provide groups adapted for platinum deposition.

Designing Structural Electrochemical Energy Storage Systems: A Perspective on the Role of Device Chemistry.

Structural energy storage devices (SESDs), designed to simultaneously store electrical energy and withstand mechanical loads, offer great potential to reduce the overall system weight in applications such as automotive, aircraft, spacecraft, marine and sports equipment. The greatest improvements will come from systems that implement true multifunctional materials as fully as possible. The realization of electrochemical SESDs therefore requires the identification and development of suitable multifunctional structural electrodes, separators, and electrolytes.

Effect of graphene flake size on functionalisation: quantifying reaction extent and imaging locus with single Pt atom tags.

Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown to depend strongly on the starting feedstock. Five characteristically different graphite sources were exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical examples were compared a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS and Raman data.

Scalable Sacrificial Templating to Increase Porosity and Platinum Utilisation in Graphene-Based Polymer Electrolyte Fuel Cell Electrodes.

Polymer electrolyte fuel cells hold great promise for a range of applications but require advances in durability for widespread commercial uptake. Corrosion of the carbon support is one of the main degradation pathways; hence, corrosion-resilient graphene has been widely suggested as an alternative to traditional carbon black. However, the performance of bulk graphene-based electrodes is typically lower than that of commercial carbon black due to their stacking effects.

Effect of silver nanospheres and nanowires on human airway smooth muscle cells: role of sulfidation.

: The toxicity of inhaled silver nanoparticles on contractile and pro-inflammatory airway smooth muscle cells (ASMCs) that control airway calibre is unknown. We explored the oxidative activities and sulfidation processes of the toxic-inflammatory response. : Silver nanospheres (AgNSs) of 20 nm and 50 nm diameter and silver nanowires (AgNWs), short S-AgNWs, 1.

Defect-Free Single-Layer Graphene by 10 s Microwave Solid Exfoliation and Its Application for Catalytic Water Splitting.

Mass production of defect-free single-layer graphene flakes (SLGFs) by a cost-effective approach is still very challenging. Here, we report such single-layer graphene flakes (SLGFs) (>90%) prepared by a nondestructive, energy-efficient, and easy up-scalable physical approach. These high-quality graphene flakes are attributed to a novel 10 s microwave-modulated solid-state approach, which not only fast exfoliates graphite in air but also self-heals the surface of graphite to remove the impurities.

Continuous Binder-Free Fibers of Pure Imogolite Nanotubes.

Imogolite nanotubes (INTs) display a range of useful properties and provide an ideal material system to study the assembly of nanomaterials into macroscopic fibers. A method of wet spinning pure, binder-free imogolite fibers has been developed using double-walled germanium imogolite nanotubes. The nanotube aspect ratio can be controlled during the initial synthesis and is critical to the spinning process.

Understanding and controlling the covalent functionalisation of graphene.

Chemical functionalisation is one of the most active areas of graphene research, motivated by fundamental science, the opportunities to adjust or supplement intrinsic properties, and the need to assemble materials for a broad array of applications. Historically, the primary consideration has been the degree of functionalisation but there is growing interest in understanding how and where modification occurs. Reactions may proceed preferentially at edges, defects, or on graphitic faces; they may be correlated, uncorrelated, or anti-correlated with previously grafted sites.

Inorganic Nanotube Mesophases Enable Strong Self-Healing Fibers.

The assembly of one-dimensional nanomaterials into macroscopic fibers can improve mechanical as well as multifunctional performance. Double-walled aluminogermanate imogolite nanotubes are geo-inspired analogues of carbon nanotubes, synthesized at low temperature, with complementary properties. Here, continuous imogolite-based fibers are wet-spun within a poly(vinyl alcohol) matrix.

Thermal Decomposition of Ternary Sodium Graphite Intercalation Compounds.

Graphite intercalation compounds (GICs) are often used to produce exfoliated or functionalised graphene related materials (GRMs) in a specific solvent. This study explores the formation of the Na-tetrahydrofuran (THF)-GIC and a new ternary system based on dimethylacetamide (DMAc). Detailed comparisons of in situ temperature dependent XRD with TGA-MS and Raman measurements reveal a series of dynamic transformations during heating.

Antibacterial Surfaces with Activity against Antimicrobial Resistant Bacterial Pathogens and Endospores.

Hospital-acquired bacterial infections are a significant burden on healthcare systems worldwide causing an increased duration of hospital stays and prolonged patient suffering. We show that polyurethane containing crystal violet (CV) and 3-4 nm zinc oxide nanoparticles (ZnO NPs) possesses excellent bactericidal activity against hospital-acquired pathogens including multidrug resistant (), , methicillin-resistant (MRSA), and even highly resistant endospores of . Importantly, we used clinical isolates of bacterial strains, a protocol to mimic the environmental conditions of a real exposure in the healthcare setting, and low light intensity equivalent to that encountered in UK hospitals (∼500 lux).

Quantification of blood-brain barrier transport and neuronal toxicity of unlabelled multiwalled carbon nanotubes as a function of surface charge.

Nanoparticles capable of penetrating the blood-brain barrier (BBB) will greatly advance the delivery of therapies against brain disorders. Carbon nanotubes hold great potential as delivery vehicles due to their high aspect-ratio and cell-penetrating ability. Studies have shown multiwalled carbon nanotubes (MWCNT) cross the BBB, however they have largely relied on labelling methods to track and quantify transport, or on individual electron microscopy images to qualitatively assess transcytosis.

One-Dimensional Pnictogen Allotropes inside Single-Wall Carbon Nanotubes.

The discovery of phosphorene, a single layer of black phosphorus, has accelerated the investigation of pnictogen nanomaterials, leading to the recent identification of arsenene and antimonene. These two-dimensional nanomaterials display physical properties superior to those of graphene for some applications. Recently, single-wall carbon nanotubes (SWCNTs) have been filled with P molecules from the melt and As molecules from the vapor phase.

Label-Free Time-of-Flight Secondary Ion Mass Spectrometry Imaging of Sulfur-Producing Enzymes inside Microglia Cells following Exposure to Silver Nanowires.

There are no methods sensitive enough to detect enzymes within cells, without the use of analyte labeling. Here we show that it is possible to detect protein ion signals of three different HS-synthesizing enzymes inside microglia after pretreatment with silver nanowires (AgNW) using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Protein fragment ions, including the fragment of amino acid (CHN = 70 amu), fragments of the sulfur-producing cystathionine-containing enzymes, and the Ag ion signal could be detected without the use of any labels; the cells were mapped using the CHN amino acid fragment.

Real-time mechanistic study of carbon nanotube anion functionalisation through open circuit voltammetry.

The mechanism of the functionalisation of reduced single walled carbon nanotubes with organobromides was monitored by open circuit voltammetry throughout the reaction and further elucidated through a series of comparative reactions. The degree of functionalisation was mapped against the reagent reduction potential, degree of electron donation of substituents (Hammett parameter), and energies calculated, , for dissociation and heterolytic cleavage of the C-Br bond. In contrast to the previously assumed reduction/homolytic cleavage mechanism, the reaction was shown to consist of a rapid association of carbon-halide bond to the reduced nanotube as a complex, displacing surface-condensed countercations, leading to an initial increase in the net nanotube surface negative charge.

Mapping the Origins of Luminescence in ZnO Nanowires by STEM-CL.

In semiconductor nanowires, understanding both the sources of luminescence (excitonic recombination, defects, etc.) and the distribution of luminescent centers (be they uniformly distributed, or concentrated at structural defects or at the surface) is important for synthesis and applications. We develop scanning transmission electron microscopy-cathodoluminescence (STEM-CL) measurements, allowing the structure and cathodoluminescence (CL) of single ZnO nanowires to be mapped at high resolution.

Depleting Depletion: Maintaining Single-Walled Carbon Nanotube Dispersions after Graft-To Polymer Functionalization.

Grafting polymers onto single-walled carbon nanotubes (SWCNTs) usefully alters properties but does not typically yield stable, solvated species directly. Despite the expectation of steric stabilization, a damaging (re)dispersion step is usually necessary. Here, poly(vinyl acetate)s (PVAc's) of varying molecular weights are grafted to individualized, reduced SWCNTs at different concentrations to examine the extent of reaction and degree of solvation.

Local Structure and Polar Order in Liquid N-Methyl-2-pyrrolidone (NMP).

N-Methyl-2-pyrrolidone (NMP) is an exceptional solvent, widely used in industry and for nanomaterials processing. Yet despite its ubiquity, its liquid structure, which ultimately dictates its solvation properties, is not fully known. Here, neutron scattering is used to determine NMP's structure in unprecedented detail.

Charged Carbon Nanomaterials: Redox Chemistries of Fullerenes, Carbon Nanotubes, and Graphenes.

Since the discovery of buckminsterfullerene over 30 years ago, sp-hybridised carbon nanomaterials (including fullerenes, carbon nanotubes, and graphene) have stimulated new science and technology across a huge range of fields. Despite the impressive intrinsic properties, challenges in processing and chemical modification continue to hinder applications. Charged carbon nanomaterials (CCNs), formed via the reduction or oxidation of these carbon nanomaterials, facilitate dissolution, purification, separation, chemical modification, and assembly.

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide.

One-Dimensional Arsenic Allotropes: Polymerization of Yellow Arsenic Inside Single-Wall Carbon Nanotubes.

The pnictogen nanomaterials, including phosphorene and arsenene, display remarkable electronic and chemical properties. Yet, the structural diversity of these main group elements is still poorly explored. Here we fill single-wall carbon nanotubes with elemental arsenic from the vapor phase.

Rectification and negative differential resistance via orbital level pinning.

A donor-acceptor system, 4-thiophenyl-azafulleroid (4TPA-C), is investigated at the point of HOMO/LUMO resonance and beyond to understand how negative differential resistance (NDR) features may be observed in such systems. Our previous investigation showed that charge transfer between the occupied and unoccupied states at resonance hindered crossing of the HOMO and LUMO levels, thus preventing the formation of an NDR feature. In this work, it is shown that the negative differential resistance feature of 4TPA-C can be tailored based on the couplings at the metal/molecule interface.