Iron-carbohydrate complexes treating iron anaemia: Understanding the nano-structure and interactions with proteins through orthogonal characterisation.

Intravenous (IV) iron-carbohydrate complexes are widely used nanoparticles (NPs) to treat iron deficiency anaemia, often associated with medical conditions such as chronic kidney disease, heart failure and various inflammatory conditions. Even though a plethora of physicochemical characterisation data and clinical studies are available for these products, evidence-based correlation between physicochemical properties of iron-carbohydrate complexes and clinical outcome has not fully been elucidated yet. Studies on other metal oxide NPs suggest that early interactions between NPs and blood upon IV injection are key to understanding how differences in physicochemical characteristics of iron-carbohydrate complexes cause variance in clinical outcomes. We therefore investigated the core-ligand structure of two clinically relevant iron-carbohydrate complexes, iron sucrose (IS) and ferric carboxymaltose (FCM), and their interactions with two structurally different human plasma proteins, human serum albumin (HSA) and fibrinogen, using a combination of cryo-scanning transmission electron microscopy (cryo-STEM), x-ray diffraction (XRD), small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS). Using this orthogonal approach, we defined the nano-structure, individual building blocks and surface morphology for IS and FCM. Importantly, we revealed significant differences in the surface morphology of the iron-carbohydrate complexes. FCM shows a localised carbohydrate shell around its core, in contrast to IS, which is characterised by a diffuse and dynamic layer of carbohydrate ligand surrounding its core. We hypothesised that such differences in carbohydrate morphology determine the interaction between iron-carbohydrate complexes and proteins and therefore investigated the NPs in the presence of HSA and fibrinogen. Intriguingly, IS showed significant interaction with HSA and fibrinogen, forming NP-protein clusters, while FCM only showed significant interaction with fibrinogen. We postulate that these differences could influence bio-response of the two formulations and their clinical outcome. In conclusion, our study provides orthogonal characterisation of two clinically relevant iron-carbohydrate complexes and first hints at their interaction behaviour with proteins in the human bloodstream, setting a prerequisite towards complete understanding of the correlation between physicochemical properties and clinical outcome.

Time-domain Tollens reaction: synthesising silver nanoparticles with the formaldehyde clock.

The addition of silver(i) ions to the methylene glycol-sulphite (MGS) clock reaction results in the sudden formation of metallic silver nanoparticles. Stable suspensions are obtained in the presence of poly(vinylpyrrolidone). The time delay before the appearance of the particles, as well as their size, decreases with the initial methylene glycol concentration while their monodispersity increases.

Targeted Additive Micromodulation of Grain Size in Nanocrystalline Copper Nanostructures by Electrohydrodynamic Redox 3D Printing.

The control of materials' microstructure is both a necessity and an opportunity for micro/nanometer-scale additive manufacturing technologies. On the one hand, optimization of purity and defect density of printed metals is a prerequisite for their application in microfabrication. On the other hand, the additive approach to materials deposition with highest spatial resolution offers unique opportunities for the fabrication of materials with complex, 3D graded composition or microstructure. As a first step toward both-optimization of properties and site-specific tuning of microstructure-an overview of the wide range of microstructure accessed in pure copper (up to >99.9 at.%) by electrohydrodynamic redox 3D printing is presented, and on-the-fly modulation of grain size in copper with smallest segments ≈400 nm in length is shown. Control of microstructure and materials properties by in situ adjustment of the printing voltage is demonstrated by variation of grain size by one order of magnitude and corresponding compression strength by a factor of two. Based on transmission electron microscopy and atom probe tomography, it is suggested that the small grain size is a direct consequence of intermittent solvent drying at the growth interface at low printing voltages, while larger grains are enabled by the permanent presence of solvent at higher potentials.

Chemical Engineering of Cu-Sn Disordered Network Metamaterials.

The design and fabrication of large-area metamaterials is an ongoing challenge. In the present work, we propose a scalable design route and low-footprint strategy for the production of large-area, frequency-selective Cu-Sn disordered network metamaterials with quasi-perfect absorption. The nanoscale networks combine the robustness of disordered systems with the broad-band optical response known from connected wire-mesh metamaterials. Using experiments and simulations, we show how frequency-selective absorption in the networks can be designed and controlled. We observe a linear dependence of the optical response as a function of Sn content ranging from the near-infrared to the visible region. The absorbing state exhibits strong sensitivity to both changes in the global network topology and the chemistry of the network. We probe the plasmonic response of these nanometric networks by electron energy loss spectroscopy (EELS), where we resolve extremely confined gap surface-plasmon (GSP) modes.

Mechanistic Understanding of Water Oxidation in the Presence of a Copper Complex by In Situ Electrochemical Liquid Transmission Electron Microscopy.

The design of molecular oxygen-evolution reaction (OER) catalysts requires fundamental mechanistic studies on their widely unknown mechanisms of action. To this end, copper complexes keep attracting interest as good catalysts for the OER, and metal complexes with TMC (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) stand out as active OER catalysts. A mononuclear copper complex, [Cu(TMC)(H2O)](NO3)2 (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), combined both key features and was previously reported to be one of the most active copper-complex-based catalysts for electrocatalytic OER in neutral aqueous solutions. However, the functionalities and mechanisms of the catalyst are still not fully understood and need to be clarified with advanced analytical studies to enable further informed molecular catalyst design on a larger scale. Herein, the role of nanosized Cu oxide particles, ions, or clusters in the electrochemical OER with a mononuclear copper(II) complex with TMC was investigated by operando methods, including in situ vis-spectroelectrochemistry, in situ electrochemical liquid transmission electron microscopy (EC-LTEM), and extended X-ray absorption fine structure (EXAFS) analysis. These combined experiments showed that Cu oxide-based nanoparticles, rather than a molecular structure, are formed at a significantly lower potential than required for OER and are candidates for being the true OER catalysts. Our results indicate that for the OER in the presence of a homogeneous metal complex-based (pre)catalyst, careful analyses and new in situ protocols for ruling out the participation of metal oxides or clusters are critical for catalyst development. This approach could be a roadmap for progress in the field of sustainable catalysis via informed molecular catalyst design. Our combined approach of in situ TEM monitoring and a wide range of complementary spectroscopic techniques will open up new perspectives to track the transformation pathways and true active species for a wide range of molecular catalysts.

3D electrohydrodynamic printing and characterisation of highly conductive gold nanowalls.

3D printing research targets the creation of nanostructures beyond the limits of traditional micromachining. A proper characterisation of their functionalities is necessary to facilitate future implementation into applications. We fabricate, in an open atmosphere, high-aspect-ratio gold nanowalls by electrohydrodynamic rapid nanodripping, and comprehensively analyse their electronic performance by four-point probe measurements. We reveal the large-grained nanowall morphology by transmission electron microscopy and explain the measured low resistivities approaching those of bulk gold. This work is a significant advancement in contactless bottom-up 3D nanofabrication and characterisation and could also serve as a platform for fundamental studies of additively manufactured high-aspect-ratio out-of-plane metallic nanostructures.

Achieving micron-scale plasticity and theoretical strength in Silicon.

As the backbone material of the information age, silicon is extensively used as a functional semiconductor and structural material in microelectronics and microsystems. At ambient temperature, the brittleness of Si limits its mechanical application in devices. Here, we demonstrate that Si processed by modern lithography procedures exhibits an ultrahigh elastic strain limit, near ideal strength (shear strength ~4 GPa) and plastic deformation at the micron-scale, one order of magnitude larger than samples made using focused ion beams, due to superior surface quality. This extended elastic regime enables enhanced functional properties by allowing higher elastic strains to modify the band structure. Further, the micron-scale plasticity of Si allows the investigation of the intrinsic size effects and dislocation behavior in diamond-structured materials. This reveals a transition in deformation mechanisms from full to partial dislocations upon increasing specimen size at ambient temperature. This study demonstrates a surface engineering pathway for fabrication of more robust Si-based structures.

Multi-metal electrohydrodynamic redox 3D printing at the submicron scale.

An extensive range of metals can be dissolved and re-deposited in liquid solvents using electrochemistry. We harness this concept for additive manufacturing, demonstrating the focused electrohydrodynamic ejection of metal ions dissolved from sacrificial anodes and their subsequent reduction to elemental metals on the substrate. This technique, termed electrohydrodynamic redox printing (EHD-RP), enables the direct, ink-free fabrication of polycrystalline multi-metal 3D structures without the need for post-print processing. On-the-fly switching and mixing of two metals printed from a single multichannel nozzle facilitates a chemical feature size of <400 nm with a spatial resolution of 250 nm at printing speeds of up to 10 voxels per second. As shown, the additive control of the chemical architecture of materials provided by EHD-RP unlocks the synthesis of 3D bi-metal structures with programmed local properties and opens new avenues for the direct fabrication of chemically architected materials and devices.

Synthesis, Spray Deposition, and Hot-Press Transfer of Copper Nanowires for Flexible Transparent Electrodes.

We report a solution-phase approach to the synthesis of crystalline copper nanowires (Cu NWs) with an aspect ratio >1000 via a new catalytic mechanism comprising copper ions. The synthesis involves the reaction between copper(II) chloride and copper(II) acetylacetonate in a mixture of oleylamine and octadecene. Reaction parameters such as the molar ratio of precursors as well as the volume ratio of solvents offer the possibility to tune the morphology of the final product. A simple low-cost spray deposition method was used to fabricate Cu NW films on a glass substrate. Post-treatment under reducing gas (5% H2 + 95% N2) atmosphere resulted in Cu NW films with a low sheet resistance of 24.5 Ω/sq, a transmittance of T = 71% at 550 nm (including the glass substrate), and a high oxidation resistance. Moreover, the conducting Cu NW networks on a glass substrate can easily be transferred onto a polycarbonate substrate using a simple hot-press transfer method without compromising on the electrical performance. The resulting flexible transparent electrodes show excellent flexibility ( R/ Ro < 1.28) upon bending to curvatures of 1 mm radius.

Nano-Sized Structurally Disordered Metal Oxide Composite Aerogels as High-Power Anodes in Hybrid Supercapacitors.

A general method for preparing nano-sized metal oxide nanoparticles with highly disordered crystal structure and their processing into stable aqueous dispersions is presented. With these nanoparticles as building blocks, a series of nanoparticles@reduced graphene oxide (rGO) composite aerogels are fabricated and directly used as high-power anodes for lithium-ion hybrid supercapacitors (Li-HSCs). To clarify the effect of the degree of disorder, control samples of crystalline nanoparticles with similar particle size are prepared. The results indicate that the structurally disordered samples show a significantly enhanced electrochemical performance compared to the crystalline counterparts. In particular, structurally disordered Ni xFe yO z@rGO delivers a capacity of 388 mAh g-1 at 5 A g-1, which is 6 times that of the crystalline sample. Disordered Ni xFe yO z@rGO is taken as an example to study the reasons for the enhanced performance. Compared with the crystalline sample, density functional theory calculations reveal a smaller volume expansion during Li+ insertion for the structurally disordered Ni xFe yO z nanoparticles, and they are found to exhibit larger pseudocapacitive effects. Combined with an activated carbon (AC) cathode, full-cell tests of the lithium-ion hybrid supercapacitors are performed, demonstrating that the structurally disordered metal oxide nanoparticles@rGO||AC hybrid systems deliver high energy and power densities within the voltage range of 1.0-4.0 V. These results indicate that structurally disordered nanomaterials might be interesting candidates for exploring high-power anodes for Li-HSCs.

Superior room-temperature ductility of typically brittle quasicrystals at small sizes.

The discovery of quasicrystals three decades ago unveiled a class of matter that exhibits long-range order but lacks translational periodicity. Owing to their unique structures, quasicrystals possess many unusual properties. However, a well-known bottleneck that impedes their widespread application is their intrinsic brittleness: plastic deformation has been found to only be possible at high temperatures or under hydrostatic pressures, and their deformation mechanism at low temperatures is still unclear. Here, we report that typically brittle quasicrystals can exhibit remarkable ductility of over 50% strains and high strengths of ∼4.5 GPa at room temperature and sub-micrometer scales. In contrast to the generally accepted dominant deformation mechanism in quasicrystals-dislocation climb, our observation suggests that dislocation glide may govern plasticity under high-stress and low-temperature conditions. The ability to plastically deform quasicrystals at room temperature should lead to an improved understanding of their deformation mechanism and application in small-scale devices.

Multidentate thioether ligands coating gold nanoparticles.

The design and synthesis of oligomeric ligands based on benzylic thioethers is presented together with their ability to enwrap and stabilize gold nanoparticles with diameters below 2 nm, which become--with increasing length of the oligomer--more monodisperse and stable.

Novel carbon nanosheets as support for ultrahigh-resolution structural analysis of nanoparticles.

The resolution in transmission electron microscopy (TEM) has reached values as low as 0.08 nm. However, these values are not accessible for very small objects in the size range of a few nanometers or lower, as they have to be placed on some support, which contributes to the overall electron-scattering signal, thereby blurring the contrast. Here, we report on the use of nanosheets made from cross-linked aromatic self-assembled monolayers as TEM sample supports. When transferred onto a copper grid, a single 1.6-nm-thick nanosheet can cover the grid and is free standing within the micron-sized openings. Despite its thinness, the sheet is stable under the impact of the electron beam. Micrographs taken from nanoclusters onto these nanosheets show highly increased contrast in comparison to the images taken from amorphous carbon supports. In scanning transmission electron microscopy with nanosheet support, a size analysis of sub-nanometer Au clusters was performed and single Au atoms were resolved.

Chain-like assembly of gold nanoparticles on artificial DNA templates via 'click chemistry'.

We present a new type of azide-functionalized gold nanoparticle and their coupling to an alkyne-modified DNA duplex using the copper(I)-catalyzed Huisgen cycloaddition ('click chemistry'), resulting in a chain-like assembly of nanoparticles on the DNA template.