Imaging Radial Distribution Functions of Complex Particles by Relayed Dynamic Nuclear Polarization.

The physical properties of many modern multi-component materials are determined by their internal microstructure. Tools capable of characterizing complex nanoscale architectures in composite materials are, therefore, essential to design materials with targeted properties. Depending on the morphology and the composition, structures may be measured by laser diffraction, scattering methods, or by electron microscopy. However, it can be difficult to obtain contrast in materials where all the components are organic, which is typically the case for formulated pharmaceuticals, or multi-domain polymers. In nuclear magnetic resonance (NMR) spectroscopy, chemical shifts allow a clear distinction between organic components and can in principle provide the required chemical contrast. Here, we introduce a method to obtain radial images of the internal structure of multi-component particles from NMR measurements of the relay of nuclear hyperpolarization obtained from dynamic nuclear polarization. The method is demonstrated on two samples of hybrid core-shell particles composed of a core of polystyrene with a shell of mesostructured silica filled with the templating agent CTAB and is shown to yield accurate images of the core-shell structures with a nanometer resolution.

Metal-Induced Crystallization in Metal Oxides.

ConspectusThe properties of a material depend upon its physical characteristics, one of these being its crystalline state. Next generation solid-state technologies will integrate crystalline oxides into thermal sensitive processes and composite materials. Crystallization of amorphous phases of metal oxides in the solid state typically requires substantial energy input to induce the amorphous to crystalline phase transformation. In the case of silica, the transformation to α-quartz in a furnace occurs above 1300 °C and that of titania, above 400 °C. These calcination processes are costly in energy but also often degrade complex material architectures or compositions.Thus, low temperature crystallization techniques are required that preserve macro- and mesostructures and complex elemental composition (e.g., organic-, metal-, and semiconductor-metal oxide hybrids/composites). Some solution-based techniques exist to directly fabricate crystalline metal oxides. However, these are not always compatible with the specificities of the system or industrial constraints. A postsynthetic, solid-state approach that reduces crystallization temperature in metal oxides is metal-induced crystallization (MIC).MIC is the introduction of catalytic amounts of a cation, which can be an s-block, p-block, or d-block cation, that migrates through the solid metal oxide lattice. The cation is thought to temporarily break metal oxide bonds, allowing [MOx] polyhedra to rotate and reform bonds with neighboring [MOx] groups in a lower energy crystalline phase. Depending on the system, the cation can favor or defavor the formation of a particular crystalline phase, providing a means to tune the purity and crystalline phase ratios. An advantage of MIC is that, although the crystallization occurs in the solid state, the crystallization process can be accomplished for particle suspensions in liquid media. In this case, the energy required to induce the crystallization can come from, for example, a microwave or an ultrasound bath. The crystallization of particles in suspension avoids aggregation from particle-particle sintering. In the case of thin films, the energy for crystallization typically comes from a laser or calcination.MIC is only recently being used as a low temperature metal oxide crystallization technique, despite being widely used in the semiconductor industry. Here, the mechanism and previous studies in MIC are presented for titania, silica, and other oxides. The beauty of this technique is that it is extremely easy to employ: cations can be incorporated into the system postsynthetically and then are often expelled from the lattice upon phase conversion. We expect MIC to enrich materials for photochromic, optoelectronic, catalyst, biological, and other applications.

Effect of Solvent on Convectively Driven Silica Particle Assembly: Decoupling Surface Tension, Viscosity, and Evaporation Rate.

The process of convectively self-assembling particles in films suffers from low reproducibility due to its high dependency on particle concentration, as well as a variety of interactions and physical parameters. Inhomogeneities in flow rates and instabilities at the air-liquid interface are mostly responsible for reproducibility issues. These problems are aggravated by adding multiple components to the dispersion, such as binary solvent mixtures or surfactant/polymer additives, both common approaches to control stick-slip behavior. When an additive is used, not only does it change the surface tension, but also the viscosity and the evaporation rate. Worse yet, gradients in these three properties can form, which then lead to Marangoni currents. Here, we use a series of alcohols to study the role of viscosity independently of other solvent properties, to show its impact on stick-slip behavior and interband distances. We show that mixtures of glycerol and alcohol or poly(acrylic acid) and alcohol lead to more complex patterning. Marangoni currents are not always observed in co-solvent systems, being dependent on the rate of solvent evaporation. To produce homogeneous particle assemblies and control stick-slip behavior, gradients must be avoided, and the surface tension and viscosity need both be carefully controlled.

Broadband Forward Light Scattering by Architectural Design of Core-Shell Silicon Particles.

A goal in the field of nanoscale optics is the fabrication of nanostructures with strong directional light scattering at visible frequencies. Here, the synthesis of Mie-resonant core-shell particles with overlapping electric and magnetic dipole resonances in the visible spectrum is demonstrated. The core consists of silicon surrounded by a lower index silicon oxynitride (SiOxNy) shell of an adjustable thickness. Optical spectroscopies coupled to Mie theory calculations give the first experimental evidence that the relative position and intensity of the magnetic and electric dipole resonances are tuned by changing the core-shell architecture. Specifically, coating a high-index particle with a low-index shell coalesces the dipoles, while maintaining a high scattering efficiency, thus generating broadband forward scattering. This synthetic strategy opens a route toward metamaterial fabrication with unprecedented control over visible light manipulation.

Microwave-Assisted and Metal-Induced Crystallization: A Rapid and Low Temperature Combination.

Here, we present a new crystallization process which, by combining microwaves and metal-induced devitrification, reduces both the time and the temperature of crystallization compared to other known methods. Titania crystallization initiates at a temperature as low as 125 °C within a few minutes of microwave radiation. Several cations induce this low-temperature crystallization, namely, Mn2+, Co2+, Ni2+, Al3+, Cu2+ and Zn2+. The crystallization mechanism is probed with electron microscopy, elemental mapping, single-particle inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and scanning Auger mapping. These techniques show that the metal ion migration through the vitreous titania under microwave radiation occurs prior to crystallization. The crystalline particles are suspended in solution at the end of the treatment, avoiding particle aggregation and sintering. The crystalline suspensions are thus ready for processing into a material or employment in any other application. This combination of microwaves and metal-induced crystallization is applied here to TiO2, but we are investigating its application to other materials as an ecofriendly crystallization method.

Nanocellulose, a Versatile Green Platform: From Biosources to Materials and Their Applications.

With increasing environmental and ecological concerns due to the use of petroleum-based chemicals and products, the synthesis of fine chemicals and functional materials from natural resources is of great public value. Nanocellulose may prove to be one of the most promising green materials of modern times due to its intrinsic properties, renewability, and abundance. In this review, we present nanocellulose-based materials from sourcing, synthesis, and surface modification of nanocellulose, to materials formation and applications. Nanocellulose can be sourced from biomass, plants, or bacteria, relying on fairly simple, scalable, and efficient isolation techniques. Mechanical, chemical, and enzymatic treatments, or a combination of these, can be used to extract nanocellulose from natural sources. The properties of nanocellulose are dependent on the source, the isolation technique, and potential subsequent surface transformations. Nanocellulose surface modification techniques are typically used to introduce either charged or hydrophobic moieties, and include amidation, esterification, etherification, silylation, polymerization, urethanization, sulfonation, and phosphorylation. Nanocellulose has excellent strength, high Young's modulus, biocompatibility, and tunable self-assembly, thixotropic, and photonic properties, which are essential for the applications of this material. Nanocellulose participates in the fabrication of a large range of nanomaterials and nanocomposites, including those based on polymers, metals, metal oxides, and carbon. In particular, nanocellulose complements organic-based materials, where it imparts its mechanical properties to the composite. Nanocellulose is a promising material whenever material strength, flexibility, and/or specific nanostructuration are required. Applications include functional paper, optoelectronics, and antibacterial coatings, packaging, mechanically reinforced polymer composites, tissue scaffolds, drug delivery, biosensors, energy storage, catalysis, environmental remediation, and electrochemically controlled separation. Phosphorylated nanocellulose is a particularly interesting material, spanning a surprising set of applications in various dimensions including bone scaffolds, adsorbents, and flame retardants and as a support for the heterogenization of homogeneous catalysts.

Air-Stable Anisotropic Monocrystalline Nickel Nanowires Characterized Using Electron Holography.

Nickel is capable of discharging electric and magnetic shocks in aerospace materials thanks to its conductivity and magnetism. Nickel nanowires are especially desirable for such an application as electronic percolation can be achieved without significantly increasing the weight of the composite material. In this work, single-crystal nickel nanowires possessing a homogeneous magnetic field are produced via a metal-organic precursor decomposition synthesis in solution. The nickel wires are 20 nm in width and 1-2 µm in length. The high anisotropy is attained through a combination of preferential crystal growth in the ⟨100⟩ direction and surfactant templating using hexadecylamine and stearic acid. The organic template ligands protect the nickel from oxidation, even after months of exposure to ambient conditions. These materials were studied using electron holography to characterize their magnetic properties. These thin nanowires display homogeneous ferromagnetism with a magnetic saturation (517 ± 80 emu cm-3), which is nearly equivalent to that of bulk nickel (557 emu cm-3). Nickel nanowires were incorporated into carbon composite test pieces and were shown to dramatically improve the electric discharge properties of the composite material.

Gold-silica quantum rattles for multimodal imaging and therapy.

Gold quantum dots exhibit distinctive optical and magnetic behaviors compared with larger gold nanoparticles. However, their unfavorable interaction with living systems and lack of stability in aqueous solvents has so far prevented their adoption in biology and medicine. Here, a simple synthetic pathway integrates gold quantum dots within a mesoporous silica shell, alongside larger gold nanoparticles within the shell's central cavity. This "quantum rattle" structure is stable in aqueous solutions, does not elicit cell toxicity, preserves the attractive near-infrared photonics and paramagnetism of gold quantum dots, and enhances the drug-carrier performance of the silica shell. In vivo, the quantum rattles reduced tumor burden in a single course of photothermal therapy while coupling three complementary imaging modalities: near-infrared fluorescence, photoacoustic, and magnetic resonance imaging. The incorporation of gold within the quantum rattles significantly enhanced the drug-carrier performance of the silica shell. This innovative material design based on the mutually beneficial interaction of gold and silica introduces the use of gold quantum dots for imaging and therapeutic applications.

Silicon-Based Dielectric Metamaterials: Focus on the Current Synthetic Challenges.

Metamaterials have optical properties that are unprecedented in nature. They have opened new horizons in light manipulation, with the ability to bend, focus, completely reflect, transmit, or absorb an incident wave front. Optically active metamaterials in particular could be used for applications ranging from 3D information storage to photovoltaic cells. Silicon (Si) particles are some of the most promising building blocks for optically active metamaterials, with high scattering efficiency coupled to low light absorption for visible frequencies. However, to date ideal Si building blocks cannot be produced by bulk synthesis techniques. The key is to find a synthetic route to produce Si building blocks between 75-200 nm in diameter of uniform size and shape, that are crystalline, have few impurities, and little to no porosity. This Review provides a theoretical background on Si optical properties for metamaterials, an overview of current synthetic methods and gives direction towards the most promising routes to ideal Si particles for metamaterials.

Size-tunable silicon nanoparticles synthesized in solution via a redox reaction.

A current challenge in silicon chemistry is to perform liquid-phase synthesis of silicon nanoparticles, which would permit the use of colloidal synthesis techniques to control size and shape. Herein we show how silicon nanoparticles were synthesized at ambient temperature and pressure in organic solvents through a redox reaction. Specifically, a hexacoordinated silicon complex, bis(N,N'-diisopropylbutylamidinato)dichlorosilane, was reduced by a silicon Zintl phase, sodium silicide (Na4Si4). The resulting silicon nanoparticles were crystalline with sizes tuned from a median particle diameter of 15 nm to 45 nm depending on the solvent. Photoluminescence measurements performed on colloidal suspensions of the 45 nm diameter silicon nanoparticles indicated a blue emission signal, attributed to the partial oxidation of the Si nanocrystals or to the presence of nitrogen impurities.

Tailoring Iridescent Visual Appearance with Disordered Resonant Metasurfaces.

The nanostructures of natural species offer beautiful visual appearances with saturated and iridescent colors, and the question arises whether we can reproduce or even create unique appearances with man-made metasurfaces. However, harnessing the specular and diffuse light scattered by disordered metasurfaces to create attractive and prescribed visual effects is currently inaccessible. Here, we present an interpretive, intuitive, and accurate modal-based tool that unveils the main physical mechanisms and features defining the appearance of colloidal disordered monolayers of resonant meta-atoms deposited on a reflective substrate. The model shows that the combination of plasmonic and Fabry-Perot resonances offers uncommon iridescent visual appearances, differing from those classically observed with natural nanostructures or thin-film interferences. We highlight an unusual visual effect exhibiting only two distinct colors and theoretically investigate its origin. The approach can be useful in the design of visual appearance with easy-to-make and universal building blocks having a large resilience to fabrication imperfections and potential for innovative coatings and fine-art applications.

Silver Nanoshells with Optimized Infrared Optical Response: Synthesis for Thin-Shell Formation, and Optical/Thermal Properties after Embedding in Polymeric Films.

We describe a new approach to making ultrathin Ag nanoshells with a higher level of extinction in the infrared than in the visible. The combination of near-infrared active ultrathin nanoshells with their isotropic optical properties is of interest for energy-saving applications. For such applications, the morphology must be precisely controlled, since the optical response is sensitive to nanometer-scale variations. To achieve this precision, we use a multi-step, reproducible, colloidal chemical synthesis. It includes the reduction of Tollens' reactant onto Sn2+-sensitized silica particles, followed by silver-nitrate reduction by formaldehyde and ammonia. The smooth shells are about 10 nm thick, on average, and have different morphologies: continuous, percolated, and patchy, depending on the quantity of the silver nitrate used. The shell-formation mechanism, studied by optical spectroscopy and high-resolution microscopy, seems to consist of two steps: the formation of very thin and flat patches, followed by their guided regrowth around the silica particle, which is favored by a high reaction rate. The optical and thermal properties of the core-shell particles, embedded in a transparent poly(vinylpyrrolidone) film on a glass substrate, were also investigated. We found that the Ag-nanoshell films can convert 30% of the power of incident near-infrared light into heat, making them very suitable in window glazing for radiative screening from solar light.

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane.

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route.

Periodic Nanoporous Inorganic Patterns Directly Made by Self-Ordering of Cracks.

Solution-processed inorganic nanoporous films are key components for the vast spectrum of applications ranging from dew harvesting to solar cells. Shaping them into complex architectures required for advanced functionality often needs time-consuming or expensive fabrication. In this work, crack formation is harnessed to pattern porous inorganic films in a single step and without using lithography. Aqueous inks, containing inorganic precursors and polymeric latexes enable evaporation-induced, defect-free periodic arrays of cracks with tunable dimensions over several centimeters. The ink formulation strategy is generalized to more than ten inorganic materials including simple and binary porous oxide and metallic films covering a whole spectrum of properties including insulating, photocatalytic, electrocatalytic, conductive, or electrochromic materials. Notably, this approach enables 3D self-assembly of cracks by stacking several layers of different compositions, yielding periodic assemblies of polygonal shapes and Janus-type patterns. The crack patterned periodic arrays of nanoporous TiO2 diffract light, and are used as temperature-responsive diffraction grating sensors. More broadly, this method represents a unique example of a self-assembly process leading to long-range order (over several centimeters) in a robust and controlled way.

Controlling disorder in self-assembled colloidal monolayers via evaporative processes.

Monolayers of assembled nano-objects with a controlled degree of disorder hold interest in many optical applications, including photovoltaics, light emission, sensing, and structural coloration. Controlled disorder can be achieved through either top-down or bottom-up approaches, but the latter is more suited to large-scale, low-cost fabrication. Disordered colloidal monolayers can be assembled through evaporatively driven convective assembly, a bottom-up process with a wide range of parameters impacting particle placement. Motivated by the photonic applications of such monolayers, in this review we discuss the quantification of monolayer disorder, and the assembly methods that have been used to produce them. We review the impact of particle and solvent properties, as well as the use of substrate patterning, to create the desired spatial distributions of particles.

Strong silica monoliths with large mesopores prepared using agarose gel templates.

Mesoporous silica pellets with controllable shape and pore size were prepared using agarose gel templates. Robust (compressive strength of 3.3-25.1 MPa), crack-free silica monoliths have been produced with large mesopores (14-23 nm), high surface areas (410-540 m(2) g(-1)), and large pore volumes (1.1-1.2 cm(3) g(-1)). The synthesis was achieved by infusing preformed agarose gels with tetraethyl orthosilicate and the nonpolar condensation catalyst tetrabutyl ammonium fluoride. The infiltrated gels were transferred to water to initiate hydrolysis and condensation of the silica precursor. Fluoride catalyzed the gelation of silica in a matter of minutes; hence, the oxide maintained the shape of the agarose pellet. The mesopore size could be modified by altering the weight percent of agarose gel used. The method employed here is simple and reproducible. As these materials have such large mesopore dimensions, they could be used as hard templates or could be specifically functionalized for use in environmental remediation, as environmentally responsive materials, biocatalysts, or catalysts.

Monitoring bisphosphonate surface functionalization and acid stability of hierarchically porous titanium zirconium oxides.

To take advantage of the full potential of functionalized transition metal oxides, a well-understood nonsilane based grafting technique is required. The functionalization of mixed titanium zirconium oxides was studied in detail using a bisphosphonic acid, featuring two phosphonic acid groups with high surface affinity. The bisphosphonic acid employed was coupled to a UV active benzamide moiety in order to track the progress of the surface functionalization in situ. Using different material compositions, altering the pH environment, and looking at various annealing conditions, key features of the functionalization process were identified that consequently will allow for intelligent material design. Loading with bisphosphonic acid was highest on supports calcined at 650 °C compared to lower calcination temperatures: A maximum capacity of 0.13 mmol g(-1) was obtained and the adsorption process could be modeled with a pseudo-second-order rate relationship. Heating at 650 °C resulted in a phase transition of the mixed binary oxide to a ternary oxide, titanium zirconium oxide in the srilankite phase. This phase transition was crucial in order to achieve high loading of the bisphosphonic acid and enhanced chemical stability in highly acidic solutions. Due to the inert nature of phosphorus-oxygen-metal bonds, materials functionalized by bisphosphonic acids showed increased chemical stability compared to their nonfunctionalized counterparts in harshly acidic solutions. Leaching studies showed that the acid stability of the functionalized material was improved with a partially crystalline srilankite phase. The materials were characterized using nitrogen sorption, X-ray powder diffraction, and UV-vis spectroscopy; X-ray photoelectron spectroscopy was used to study surface coverage with the bisphosphonic acid molecules.

Hybrid rigid/soft and biologic/synthetic materials: polymers grafted onto cellulose microcrystals.

Rigid nanoscale polymer rods were prepared by grafting preformed amine-terminated poly(styrene) and poly(tert-butyl acrylate) onto oxidized cellulose microcrystals. Low polydispersity polymers, grown using atom transfer radical polymerization, were characterized and purified prior to cellulose attachment. Oxidation of the cellulose microcrystal led to the formation of carboxylic acids on the surface of the microcrystals. Covalent attachment of the polymers onto the cellulose microcrystals was achieved via a carbodiimide-mediated amidation reaction. The length and diameter of the polymer-cellulose composites increased upon surface modification. Typically, polymer-cellulose composites are synthesized by a grafting-from method because it can be difficult to obtain sufficient graft density using a grafting-to preparation. However, the composites reported here comprised 60-64% grafted polymer by mass. This degree of grafting-to allowed the composite to form stable suspensions in organic solvents.

Seeded growth of ultrathin gold nanoshells using polymer additives and microwave radiation.

Nanoshells made of a silica core and a gold shell possess an optical response that is sensitive to nanometer-scale variations in shell thickness. The exponential red shift of the plasmon resonance with decreasing shell thickness makes ultrathin nanoshells (less than 10 nm) particularly interesting for broad and tuneable ranges of optical properties. Nanoshells are generally synthesised by coating gold onto seed-covered silica particles, producing continuous shells with a lower limit of 15 nm, due to an inhomogeneous droplet formation on the silica surface during the seed regrowth. In this paper, we investigate the effects of three variations of the synthesis protocol to favour ultrathin nanoshells: seed density, polymer additives and microwave treatment. We first maximised gold seed density around the silica core, but surprisingly its effect is limited. However, we found that the addition of polyvinylpyrrolidone during the shell synthesis leads to higher homogeneity and a thinner shell and that a post-synthetic thermal treatment using microwaves can further smooth the particle surface. This study brings new insights into the synthesis of metallic nanoshells, pushing the limits of ultrathin shell synthesis.

Size matters: incorporation of poly(acrylic acid) and small molecules into hierarchically porous metal oxides prepared with and without templates.

Template synthesis of metal oxides can create materials with highly controlled and reproducible pore structures that can be optimized for particular applications. Zirconium titanium oxides (25:75 mol %) with three different pore structures were synthesized in order to relate polymer loading capacity to macropore architecture. Sol-gel chemistry was used to prepare the materials in conjunction with (i) agarose gel templating, (ii) no template, and (iii) stearic acid templating. The three materials possessed high surface areas (212-316 m(2) g(-1)). Surface modification was performed postsynthetically using propionic acid (a monomer), glutaric acid (a dimer), and three molecular weights of poly(acrylic acid) (2000, 100,000, and 250,000 g mol(-1)). Higher loading (mg g(-1)) was observed for the polymers than for the small molecules. Following surface modification, a perceptible decrease in surface area and mesopore volume was noted, but both mesoporosity and macroporosity were retained. The pore architecture had a strong bearing on the quantity and rate of polymer incorporation into metal oxides. The templated pellet with hierarchical porosity outperformed the nontemplated powder and the mesoporous monolith (in both loading capacity and surface coverage). The materials were subjected to irradiation with (60)Co gamma-rays to determine the radiolytic stability of the inorganic support and the hybrid material containing the monomer, dimer, and polymer. The polymer and the metal oxide substrate demonstrated notable radiolytic stability.