High brightness amine‐terminated silicon nanocrystals (Si NCs) have been utilized in a simple and rapid assay for the highly selective and sensitive detection of Fe3+ via quenching of their strong blue luminescence, without the need for analyte‐specific labeling groups. Sensitive detection of Fe3+ is successfully demonstrated, with a linear relationship observed between luminescence quenching and Fe3+ concentration from 5 × 10−6 to 900 × 10−6m and a limit of detection of 1.3 × 10−6m. The Si NCs show excellent selectivity toward Fe3+ ions, with no quenching of the luminescence signal induced by the presence of Fe2+ ions, allowing for solution phase discrimination between the ionic species in different charge states.

A room temperature, solution phase method for production of size monodisperse germanium nanocrystals (Ge NCs) terminated with different chemical functionalities (epoxy, acetate, amine, carboxylic acid, and alkyl) is reported. Ge NC photoluminescence spectra show that the emission can be tuned from the UV to the blue/green through choice of ligand. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Vibration energy harvesters typically have a narrow bandwidth, which allows them to generate high amounts of power, but only at a specific frequency. This paper presents a novel method of increasing the bandwidth of a cantilever beam by creating a non-uniform load. The concept uses a liquid filled mass, which causes the structures overall centre of gravity to shift as the beam bends. The overall centre of gravity shifts due to the mass change caused by the dynamic behaviour of the fluid. This paper validates the concept both numerically and experimentally by using a custom manufactured fluid filled mass on a piezoelectric cantilever. A water filled mass demonstrated a 2.8x increase in bandwidth for low acceleration (<1 g) and low frequency cantilever (27 Hz) devices. The effects due to liquid density and liquid viscosity are also experimentally measured. The numerical estimations match well with the experimental results for low accelerations (<0.5 g). Above 0.5 g acceleration the liquid water used in the cavity became chaotic, which caused liquid droplets to separate from the bulk liquid, thus reducing the overall mass for given point in time. This non-linear liquid dynamic behaviour further increases the bandwidth by creating a larger variation in the resonant frequency. In addition, as the fluid viscosity increases, the acceleration from the vibration source required to cause movement in the fluid also increases. The measured open circuit peak to peak voltage demonstrated an increase in bandwidth without significant loss in voltage. (C) 2016 Elsevier B.V. All rights reserved.

Germanium nanocrystals (Ge NCs) have attracted increasing attention as a promising alternative to II–VI and IV–VI semiconductor materials as they are cheap, “green,” electrochemically stable, and compatible with existing CMOS processing methods. Germanium is a particularly attractive material for optoelectronic applications as it combines a narrow band gap with high carrier mobilities and a large exciton Bohr radius. Solution-phase synthesis and characterisation of size monodisperse alkyl-terminated Ge NCs are demonstrated. Ge NCs were synthesised under inert atmospheric conditions via the reduction of Ge halide salts (GeX 4 ) by hydride reducing agents within inverse micelles. Regulation of NC size is achieved by variation of germanium precursor and the strength of hydride reducing agents used. UV-Visible absorbance and photoluminescence spectroscopy showed strong significant quantum confinement effects, with moderate absorption in the UV spectral range, and strong emission in the violet with a marked dependence on excitation wavelength.

Nanocomposite films were successfully grown by aerosol-assisted chemical vapour deposition (CVD) in a single deposition step using a mixture of Indium Tin neodecanoate and ligand stabilised silicon nanocrystals. Samples were analysed by HRTEM and silicon nanocrystals with a density of 1.2 × 1012 cm-2 were observed. From the reconstructed 3D tomogram, the averaged distance between the nearest nanoparticles is 8.3 nm and the 3D density of nanoparticles is 1.6 × 1018 cm-3. An animation of the 3D reconstruction is supplied in the supporting information. These data show the versatility of aerosol assisted CVD in achieving a nanocomposite with such a density of silicon nanocrystals, of carefully controlled size and shape, within a polycrystalline host matrix. Therefore, meeting the density and size distribution requirements of particle inclusion in active nanocomposites for photovoltaic structures

Luminescent water-soluble germanium nanocrystals (Ge NCs) have been developed as a fluorescent sensing platform for the highly selective and sensitive detection of Fe3+ via quenching of their strong blue luminescence, without the need for analyte-specific labelling groups. The amine-terminated Ge NCs were separated into two discrete size fractions with average diameters of 3.9±0.4 nm and 6.8±1.8 nm using centrifugation. The smaller 3.9 nm NCs possessed a strong blue luminescence, with an average lifetime of 6.1 ns and a quantum yield (QY) of 21.5%, which is strongly influenced by solution pH. In contrast, 6.8 nm NCs exhibited a green luminescence with a longer lifetime of 7.8 ns and lower QY (6.2%) that is insensitive to pH. Sensitive detection of Fe3+ was successfully demonstrated, with a linear relationship between luminescence quenching and Fe3+ concentration observed from 0-800 μM, with a limit of detection of 0.83 μM. The Ge NCs show excellent selectivity toward Fe3+ ions, with no quenching of the fluorescence signal induced by the presence of Fe2+ ions, allowing for solution phase discrimination between ions of the same element with different formal charges. The luminescence quenching mechanism was confirmed by static and time-resolved photoluminescence spectroscopies, while the applicability for this assay for detection of Fe3+ in real water samples was successfully demonstrated.

Optical detection of volatile electron deficient analytes via fluorescence quenching is demonstrated using ca. 200 nm diameter template-synthesized polyfluorene nanofibers as nanoscale detection elements. Observed trends in analyte quenching effectiveness suggest that, in addition to energetic factors, analyte vapor pressure and polymer/analyte solubility play an important role in the emission quenching process. Individual nanofibers successfully act as luminescent reporters of volatile nitroaromatics at sub-parts per million levels. Geometric factors, relating to the nanocylindrical geometry of the fibers and to low nanofiber substrate coverage, providing a less crowded environment around fibers, appear to play a role in providing access by electron deficient quencher molecules to the excited states within the fibers, thereby facilitating the pronounced fluorescence quenching response.

Publisher Rights Statement: NOTICE: this is the author’s version of a work that was accepted for publication. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published as Hu, W., Culloty, S., Darmody, G., Lynch, S., Davenport, J., Ramirez-Garcia, S., Dawson, K., Lynch, I., Doyle, H., Sheehan, D., Neutral red retention time assay in determination of toxicity of nanoparticles, Marine Environmental Research (2015), doi: 10.1016/j.marenvres.2015.05.007. Birmingham

Recent decades have seen a strong increase in the promise and uses of nanotechnology. This is correlated with their growing release in the environment and there is concern that nanomaterials may endanger ecosystems. Silver nanoparticles (AgNPs) have some of the most varied applications, making their release into the environment unavoidable. In order to assess their potential toxicity in aquatic environments, the acute toxicity of citrate-coated AgNPs to Daphnia magna was measured and compared to that of AgNO3. AgNPs were found to be ten times less toxic by mass than silver ions, and most of this toxicity was removed by ultracentrifuging. At the protein level, the two forms of silver had different impacts. Both increased protein thiol content, while only AgNP increased carbonyl levels. In 2DE of samples labelled for carbonyls, no feature was significantly affected by both compounds, indicating different modes of toxicity. Identified proteins showed functional overlap between the two compounds: vitellogenins (vtg) were present in most features identified, indicating their role as a general stress sensor. In addition to vtg, hemoglobin levels were increased by the AgNP exposure while 14-3-3 protein (a regulatory protein) carbonylation levels were reduced by AgNO3. Overall, this study confirms the previously observed lower acute toxicity of AgNPs, while demonstrating that the toxicity of both forms of silver follow somewhat different biologic pathways, potentially leading to different interactions with natural compounds or pollutants in the aquatic environment.

A sacrificial polymer templating, simple chemical etching and AACVD is described for the fabrication of robust, large area 3D inverse opals patterned with silicon nanocrystals.

Alkyl-terminated silicon nanocrystals (Si NCs) are synthesized at room temperature by hydride reduction of silicon tetrachloride (SiCl₄) within inverse micelles. Highly monodisperse Si nanocrystals with average diameters ranging from 2 to 6 nm are produced by variation of the cationic quaternary ammonium salts used to form the inverse micelles. Transmission electron microscopy imaging shows that the NCs are highly crystalline, while FTIR spectra confirm that the NCs are passivated by covalent attachment of alkanes, with minimal surface oxidation. UV-vis absorbance and photoluminescence spectroscopy show significant quantum confinement effects, with moderate absorption in the UV spectral range, and a strong blue emission with a marked dependency on excitation wavelength. The photoluminescence quantum yield (Φ) of the Si NCs exhibits an inverse relationship with the mean NC diameter, with a maximum of 12% recorded for 2 nm NCs.

Highly luminescent germanium nanocrystals (NCs) are synthesized at room temperature by hydride reduction of germanium tetrachloride (GeCl4) within inverse micelles. Regulation of the Ge NC size is achieved by varying the alkyl chain length of the cationic quaternary ammonium surfactants used to form the inverse micelles. The Ge NCs are chemically passivated with allylamine ligands using a Pt-catalyzed hydrogermylation reaction, minimizing surface oxidation while rendering the NCs dispersible in a range of polar solvents. Transmission electron microscopy shows that the NCs are highly crystalline with well-defined core diameters tuned from 3 to 5 nm. UV-Vis absorbance and photoluminescence (PL) spectroscopy show significant quantum confinement effects, with moderate absorption in the UV spectral range, and a strong, narrow luminescence in the visible with a marked dependency on excitation wavelength. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases to 4.5 nm.

Highly luminescent carbon quantum dots (CQDs) are synthesized at room temperature by hydride reduction of carbon tetrachloride (CCl4) within inverse micelles. Regulation of the average diameter of the allylamine terminated CQDs is achieved by varying the strength of the reducing agent used. Transmission electron microscopy shows that the NCs are highly crystalline with well-defined core diameters tuned from 2 to 6 nm, while FTIR and XPS spectroscopy confirm that the CQDs possess similar surface chemistry. UV-Vis and PL spectroscopy show significant quantum confinement effects, with moderate absorption in the UV spectral range, and a strong, narrow luminescence in the visible with a marked dependency on excitation wavelength. Time resolved photoluminescence measurements showed lifetimes for all CQDs in the ns range, while a maximum PL quantum yield of 27% is observed for the CQDs.

Highly luminescent water soluble carbon quantum dots (CQDs) with narrow size distributions have been prepared via a simple room temperature, solution-phase synthesis. The CQDs, stabilised by covalently bound allylamine ligands to minimise surface oxidation, exhibit an excitation wavelength dependent blue luminescence with a quantum yield of 25%.

An efficient one-pot method for fabricating alkyl-capped germanium nanocrystals (Ge NCs) is reported. Ge NCs with a size of 3.9 ± 0.5 nm, are formed by co-reduction of germanium tetrachloride in the presence of n-butyltrichlorogermane, producing NCs with butyl-terminated surfaces. The advantage of this method is that it allows rapid synthesis and functionalisation of NCs with minimal post-synthetic purification requirements. TEM imaging showed that the Ge NCs are monodisperse and highly crystalline, while EDX and SAED confirmed the chemical identity and crystal phase of the NCs. FTIR and XPS confirmed that the Ge NCs were well passivated, with some oxidation of the nanocrystal surface. Optical spectroscopy of the NCs showed a strong absorbance in the UV region and an excitation wavelength dependent photoluminescence in the UV/violet. Time resolved photoluminescence measurements showed the presence of two nanosecond lifetime components, consistent with recombination of photogenerated excitons at low lying energy states present at the nanocrystal surface. Photoluminescence quantum yields were determined to be 37 %, one of the highest values reported for organically terminated Ge NCs.

Novel processes were developed for fabricating silicon nanocrystals and nanocomposite materials which could be used as absorbers in third generation photovoltaic devices. A conventional high-temperature annealing technique was studied as a reference process, with some new insights in crystallisation mechanisms. Innovative methods for silicon nanocrystal synthesis at much lower temperature were demonstrated, namely chemical vapour deposition (CVD), physical vapour deposition (PVD) and aerosol-assisted CVD. Besides the advantage of low substrate temperature, these new techniques allow to fabricate silicon nanocrystals embedded in wide bandgap semiconductor host matrices, with a high density and a narrow size dispersion.

Highly luminescent carbon quantum dots (CQDs) with narrow size distributions were synthesised in reverse micelles using a simple room temperature, solution-phase synthesis. The CQDs are stabilised by covalently bound alkyl ligand to minimise surface oxidation and exhibit blue emission with a marked dependency on excitation wavelength.

Alkyl-terminated Si x G 1-x nanocrystals are prepared at room temperature by co-reduction of Si and Ge precursors by hydride reducing agents within inverse micelles. Compositional control of the alloy silicon-germanium NCs ( ca. 3.6 nm) is achieved by varying the relative amounts of each precursor used in the synthesis. Transmission electron microscopy imaging confirmed that the NCs are highly crystalline with a narrow size distribution; optical spectroscopy shows strong quantum confinement effects, with moderate absorption in the UV spectral range, and a strong blue emission with a marked dependency on excitation wavelength.