Surface functionalities of gold nanoparticles impact embryonic gene expression responses.

Incorporation of gold nanoparticles (AuNPs) into consumer products is increasing; however, there is a gap in available toxicological data to determine the safety of AuNPs. In this study, we utilised the embryonic zebrafish to investigate how surface functionalisation and charge influence molecular responses. Precisely engineered AuNPs with 1.5 nm cores were synthesised and functionalized with three ligands: 2-mercaptoethanesulfonic acid (MES), N,N,N-trimethylammoniumethanethiol (TMAT), or 2-(2-(2-mercaptoethoxy)ethoxy)ethanol. Developmental assessments revealed differential biological responses when embryos were exposed to the functionalised AuNPs at the same concentration. Using inductively coupled plasma-mass spectrometry, AuNP uptake was confirmed in exposed embryos. Following exposure to MES- and TMAT-AuNPs from 6 to 24 or 6 to 48 h post fertilisation, pathways involved in inflammation and immune response were perturbed. Additionally, transport mechanisms were misregulated after exposure to TMAT and MES-AuNPs, demonstrating that surface functionalisation influences many molecular pathways.

Single nanoscale cluster species revealed by 1H†NMR diffusion-ordered spectroscopy and small-angle X-ray scattering.

A solved structure: The hydrated Ga(13) cluster, [Ga(13)(µ(3)-OH)(6)(µ-OH)(18)(H(2)O)(24)](NO(3))(15)], persists as a discrete nanoscale structure in an aqueous polar solvent at millimolar concentration. SAXS data confirm the presence of Ga(13) in dimethyl sulfoxide (DMSO). In aqueous [D(6)]DMSO (1)H NMR signals for the hydroxo and aquo ligands of Ga(13) were detected, thus showing a cluster with a hydrodynamic radius of (11.2±0.8) Š(see picture).

Media ionic strength impacts embryonic responses to engineered nanoparticle exposure.

Embryonic zebrafish were used to assess the impact of solution ion concentrations on agglomeration and resulting in vivo biological responses of gold nanoparticles (AuNPs). The minimum ion concentration necessary to support embryonic development was determined. Surprisingly, zebrafish exhibit no adverse outcomes when raised in nearly ion-free media. During a rapid throughput screening of AuNPs, 1.2-nm 3-mercaptopropionic acid-functionalized AuNPs (1.2-nm 3-MPA-AuNPs) rapidly agglomerate in exposure solutions. When embryos were exposed to 1.2-nm 3-MPA-AuNPs dispersed in low ionic media, both morbidity and mortality were induced, but when suspended in high ionic media, there was little to no biological response. We demonstrated that the media ionic strength greatly affects agglomeration rates and biological responses. Most importantly, the insensitivity of the zebrafish embryo to external ions indicates that it is possible, and necessary, to adjust the exposure media conditions to optimize NP dispersion prior to assessment.

One-step Melt Synthesis of Water Soluble, Photoluminescent, Surface-Oxidized Silicon Nanoparticles for Cellular Imaging Applications.

We have developed a versatile, one-step melt synthesis of water-soluble, highly emissive silicon nanoparticles using bi-functional, low-melting solids (such as glutaric acid) as reaction media. Characterization through transmission electron microscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy shows that the one-step melt synthesis produces nanoscale Si cores surrounded by a silicon oxide shell. Analysis of the nanoparticle surface using FT-IR, zeta potential, and gel electrophoresis indicates that the bi-functional ligand used in the one-step synthesis is grafted onto the nanoparticle, which allows for tuning of the particle surface charge, solubility, and functionality. Photoluminescence spectra of the as-prepared glutaric acid-synthesized silicon nanoparticles show an intense blue-green emission with a short (ns) lifetime suitable for biological imaging. These nanoparticles are found to be stable in biological media and have been used to examine cellular uptake and distribution in live N2a cells.

The nanomaterial characterization bottleneck.

The future of nanotechnology rests upon approaches to making new, useful nanomaterials and testing them in complex systems. Currently, the advance from discovery to application is constrained in nanomaterials relative to a mature market, as seen in molecular and bulk matter. To reap the benefits of nanotechnology, improvements in characterization are needed to increase throughput as creativity outpaces our ability to confirm results. The considerations of research, commerce, and regulation are part of a larger feedback loop that illustrates a mutual need for rapid, easy, and standardized characterization of a large property matrix. Now, we have an opportunity and a need to strike a new balance that drives higher quality research, simplifies commercial exploitation, and allows reasoned regulatory approaches.

Ordered mesoporous silicon through magnesium reduction of polymer templated silica thin films.

This paper describes the process of making ordered mesoporous silicon (Si) thin films. The process begins with mesoporous silica (SiO 2) thin films that are produced via evaporation induced self-assembly (EISA) using sol-gel silica precursors with a diblock copolymer template. This results in a film with a cubic lattice of 15 nm diameter pores and 10 nm thick walls. The silicon is produced through reduction of the silica thin films in a magnesium (Mg) vapor at 675 degrees C. Magnesium reduction preserves the ordered pore-solid architecture but replaces the dense silica walls with 10-17 nm silicon crystallites. The resulting porous silicon films are characterized by a combination of low and high angle X-ray diffraction, combined with direct SEM imaging. The result is a straightforward route to the production of ordered nanoporous silicon.

Vertically oriented hexagonal mesoporous films formed through nanometre-scale epitaxy.

Polymer- and surfactant-templated mesoporous inorganic materials offer a unique combination of controllable nanoscale architecture, materials variation and low-cost solution processing. Inorganic materials can be produced with a range of periodic pore structures, with feature size ranging from 2 to 30 nm, and from a diverse set of materials. Unfortunately in thin-film form, the pores of the ubiquitous hexagonal honeycomb phase tend to lie in the plane of the substrate making these materials unsuitable for applications where diffusion into the pores is required. Here, we show that nanometre-scale epitaxy on a patterned substrate can be used to form vertically oriented pores in honeycomb-structured films. We use the surface of cubic mesoporous films to form the pattern; as such, our method does not sacrifice the simple processing advantages of a self-assembled system. A precise lattice match between the hexagonal and cubic films is needed for vertical orientation, a condition that can be achieved using mixed templates or selective pore swelling. Pore orientation is characterized by a combination of microscopy and diffraction. Here, we present alignment data on oriented nanopores in the 10-15 nm range, but the method should be applicable across the 2-30 nm pore size range of these self-organized materials.

Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters.

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.