Hugh Doyle

Colloidal synthesis of nanocrystals and nanocrystal superlattices

This paper provides an overview of the synthetic techniques used to prepare colloidal nanocrystals (NCs) of controlled composition, size, shape, and internal structure and the methods for manipulat...

Oxidative stress and toxicity of gold nanoparticles in Mytilus edulis

Gold nanoparticles (AuNP) have potential applications in drug delivery, cancer diagnosis and therapy, food industry and environment remediation. However, little is known about their potential toxicity or fate in the environment. Mytilus edulis was exposed in tanks to 750 ppb AuNP (average diameter 5.3 ± 1 nm) for 24h to study in vivo biological effects of nanoparticles. Traditional biomarkers and an affinity procedure selective for thiol-containing proteins followed by two-dimensional electrophoresis (2DE) separations were used to study toxicity and oxidative stress responses. Results were compared to those obtained for treatment with cadmium chloride, a well known pro-oxidant. M. edulis mainly accumulated AuNP in digestive gland which also showed higher lipid peroxidation. One-dimensional SDS/PAGE (1DE) and 2DE analysis of digestive gland samples revealed decreased thiol-containing proteins for AuNP. Lysosomal membrane stability measured in haemolymph gave lower values for neutral red retention time (NRRT) in both treatments but was greater in AuNP. Oxidative stress occurred within 24h of AuNP exposure in M. edulis. Previously we showed that larger diameter AuNP caused modest effects, indicating that nanoparticle size is a key factor in biological responses to nanoparticles. This study suggests that M. edulis is a suitable model animal for environmental toxicology studies of nanoparticles.

Gold nanoparticles and oxidative stress in Mytilus edulis

Little is known about potential environmental impact of nanoparticles. Gold nanoparticles can cause unexpected biological responses. Here, Mytilus edulis were exposed (24h) to gold-citrate nanoparticles (GNP), menadione and both compounds simultaneously (GNP/menadione). Protein ubiquitination and carbonylation were determined in gill, mantle and digestive gland, along with traditional oxidative stress biomarkers; catalase activity and neutral red retention time assay (haemolymph). 2DE gels were performed on gill proteins (menadione; GNP/menadione). Our results reveal that GNP may induce oxidative stress.

Exposure of the blue mussel, Mytilus edulis, to gold nanoparticles and the pro-oxidant menadione

Relatively little is known about how gold nanoparticles (GNP) might interact in vivo with marine organisms. Mytilus edulis was exposed (24h) to approximately 15 nm GNP, menadione and both compounds simultaneously (GNP/menadione). GNP was detected by inductively coupled plasma-optical emission spectroscopy mainly in digestive gland of samples exposed to GNP though not GNP/menadione, perhaps due to impaired feeding. Thioredoxin reductase activity and malondialdehyde levels were determined in all tissues. Thioredoxin reductase inhibition was detected only in digestive gland exposed to menadione whilst malondialdehyde levels did not vary in response to treatment in all tissues. GNP caused a decrease in the reduced/oxidized glutathione ratio in digestive gland, but no difference was found in other tissues or for other treatments. One dimensional electrophoresis of proteins containing thiol groups was performed in all tissues and revealed a reduction in protein thiols for all treatments in digestive gland. Two dimensional electrophoresis of digestive gland extracts, from GNP and control groups, showed decreased levels of thiol proteins in response to GNP which we attribute to oxidation. Our results suggest that GNP causes a modest level of oxidative stress sufficient to oxidize thiols in glutathione and proteins but without causing lipid peroxidation or induction of thioredoxin reductase activity.

Near-infrared electroluminescent devices based on colloidal HgTe quantum dot arrays

Crystalline 4.6 nm HgTe quantum dots, stabilized by 1-thioglycerol ligands, were synthesized by wet chemical methods. Room-temperature photoluminescence spectra of the dots, both in solution and as solid arrays, exhibited near-infrared emission. Light-emitting devices were fabricated by deposition of quantum dot layers onto glass∕indium tin oxide (ITO)∕3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates followed by top contacting with evaporated aluminum. Room-temperature near-infrared electroluminescence from 1mm2 ITO∕PEDOT∕HgTe∕Al devices, centered at ∼1600nm, with an external quantum efficiency of 0.02% and brightness of 150nW∕mm2 at 50 mA and 2.5 V was achieved.

Controlled Assembly of Monodisperse ε-Cobalt-Based Nanocrystals

General synthetic routes to monodisperse c-cobalt (β-Mn type phase) nanocrystals (e-Co) and controlled assembly of these nanocrystals are presented in this paper. The e-Co particles are obtained by superhydride reduction of cobalt chloride (anhydrous or hexahydrate) in a high temperature solution phase (200°C) in the presence of a combination of long chain diol, oleic acid and trialkylphosphine. Monodisperse nanocrystals are isolated by size selective precipitation. As synthesized cobalt particles are each a single crystal with a complex cubic structure related to the beta phase of elemental manganese (β-Mn). Self-assembly of these uniform cobalt particles on solid substrates is induced by evaporation of the carrier solvent producing 2-D and 3-D magnetic superlattices. Annealing of assembled e-Co nanocrystal arrays converts them to the hcp cobalt crystal arrays. The inter-particle distance can be adjusted by selected thermal treatments or by chemical ligand exchange. This control over particle dimensions, crystallinity and assembly offers a model system for the study of ultra-high density recording media.

Proteomic evaluation of citrate-coated silver nanoparticles toxicity in Daphnia magna

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.

Synthesis of Oligonucleotides Carrying Anchoring Groups and Their Use in the Preparation of Oligonucleotide–Gold Conjugates

Oligodeoxynucleotide conjugates 1–15 carrying anchoring groups such as amino, thiol, pyrrole, and carboxy groups were prepared. A post-synthetic modification protocol was developed. In this method 2′-deoxy-O4-(p-nitrophenyl)uridine-3-phosphoramidite was prepared and incorporated in oligonucleotides. After assembly, the modified nucleoside was made to react with different amines carrying the anchoring groups. At the same time, protecting groups were removed to yield the desired oligonucleotide conjugates. In a second approach, amino, thiol, and carboxylic groups were introduced into the 3′-end of the oligonucleotides by preparing solid supports loaded with the appropriate amino acids. Oligonucleotidegold conjugates were prepared and their binding properties were examined.

Efficient one-pot synthesis of highly monodisperse carbon quantum dots

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.

Size controlled synthesis of carbon quantum dots using hydride reducing agents

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.