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Gold nanorods are one of the most widely explored inorganic materials in nanomedicine for diagnostics, therapeutics and sensing1. It has been shown that gold nanorods are not cytotoxic and localize within cytoplasmic vesicles following endocytosis, with no nuclear localization2,3, but other studies have reported alterations in gene expression profiles in cells following exposure to gold nanorods, via unknown mechanisms4. In this work we describe a pathway that can contribute to this phenomenon. By mapping the intracellular chemical speciation process of gold nanorods, we show that the commonly used Au–thiol conjugation, which is important for maintaining the noble (inert) properties of gold nanostructures, is altered following endocytosis, resulting in the formation of Au(i)–thiolates that localize in the nucleus5. Furthermore, we show that nuclear localization of the gold species perturbs the dynamic microenvironment within the nucleus and triggers alteration of gene expression in human cells. We demonstrate this using quantitative visualization of ubiquitous DNA G-quadruplex structures, which are sensitive to ionic imbalances, as an indicator of the formation of structural alterations in genomic DNA. The release of nuclear-localizing gold species from intracellular gold nanorods may alter gene expression on interaction with the genomic DNA.

Production of radionuclide-free copper concentrates is dependent on understanding and controlling the deportment of daughter radionuclides (RNs) produced from 238U decay, specifically 226Ra, 210Pb, and 210Po. Sulfuric acid leaching is currently employed in the Olympic Dam processing plant (South Australia) to remove U and fluorine from copper concentrates prior to smelting but does not adequately remove the aforementioned RN. Due to chemical similarities between lead and alkaline earth metals (including Ra), two sets of experiments were designed to understand solution interactions between Sr, Ba, and Pb at various conditions. Nanoscale secondary ion mass spectrometry (NanoSIMS) isotopic spatial distribution maps and laser ablation inductively coupled-plasma mass spectrometry transects were performed on laboratory-grown crystals of baryte, celestite, and anglesite which had been exposed to different solutions under different pH and reaction time conditions. Analysis of experimental products reveals three uptake mechanisms: overgrowth of nearly pure SrSO4 and PbSO4 on baryte; incorporation of minor of Pb and Ba into celestite due to diffusion; and extensive replacement of Pb by Sr (and less extensive replacement of Pb by Ba) in anglesite via coupled dissolution-reprecipitation reactions. The presence of H2SO4 either enhanced or inhibited these reactions. Kinetic modelling supports the experimental results, showing potential for extrapolating the (Sr, Ba, Pb)SO4 system to encompass RaSO4. Direct observation of grain-scale element distributions by nanoSIMS aids understanding of the controlling conditions and mechanisms of replacement that may be critical steps for Pb and Ra removal from concentrates by allowing construction of a cationic replacement scenario targeting Pb or Ra, or ideally all insoluble sulfates. Experimental results provide a foundation for further investigation of RN uptake during minerals processing, especially during acid leaching. The new evidence enhances understanding of micro- to nanoscale chemical interactions and not only aids determination of where radionuclides reside during each processing stage but also guides development of flowsheets targeting their removal.

Platinum-group elements are strategically important metals. Finding new deposits is becoming increasingly difficult owing to our limited understanding of the processes that affect their mobility in surface environments. Microorganisms have been shown to promote the mobility of metals around ore deposits. Here we show that microorganisms influence the mobility of platinum-group elements in mineral grains collected from Brazil, Australia and Colombia. Scanning electron microscopy showed biofilms covering the platinum-group mineral grains. The biofilms contained abundant platinum-group element nanoparticles and microcrystalline aggregates, and were dominated by Proteobacteria, many of which were closely related to known metal-resistant species. Some platinum-group mineral grains contained carbon, nitrogen, sulfur, selenium and iodine, suggesting the grains may be biogenic in origin. Molecular analyses show that Brazilian platinum–palladium grains hosted specific bacterial communities, which were different in composition from communities associated with gold grains, or communities in surrounding soils and sediments. Nano-phase metallic platinum accumulated when a metallophillic bacterium was incubated with a percolating platinum-containing medium, suggesting that biofilms can cause the precipitation of mobile platinum complexes. We conclude that biofilms are capable of forming or transforming platinum-group mineral grains, and may play an important role for platinum-group element dispersion and re-concentration in surface environments.

Following injury to the central nervous system, axons and myelin distinct from the initial injury site undergo changes associated with compromised function. Quantifying such changes is important to understanding the pathophysiology of neurotrauma; however, most studies to date used 2 dimensional (D) electron microscopy to analyse single sections, thereby failing to capture changes along individual axons. We used serial block face scanning electron microscopy (SBF SEM) to undertake 3D reconstruction of axons and myelin, analysing optic nerves from normal uninjured female rats and following partial optic nerve transection. Measures of axon and myelin dimensions were generated by examining 2D images at 5 µm intervals along the 100 µm segments. In both normal and injured animals, changes in axonal diameter, myelin thickness, fiber diameter, G-ratio and percentage myelin decompaction were apparent along the lengths of axons to varying degrees. The range of values for axon diameter along individual reconstructed axons in 3D was similar to the range from 2D datasets, encompassing reported variation in axonal diameter attributed to retinal ganglion cell diversity. 3D electron microscopy analyses have provided the means to demonstrate substantial variability in ultrastructure along the length of individual axons and to improve understanding of the pathophysiology of neurotrauma.

Diazotrophic bacteria are instrumental in generating biologically usable forms of nitrogen by converting abundant dinitrogen gas (N-2) into available forms, such as ammonium. Although nitrogen is crucial for coral growth, direct observation of associations between diazotrophs and corals has previously been elusive. We applied fluorescence in situ hybridization (FISH) and nanoscale secondary ion mass spectrometry to observe the uptake of N-15-enriched diazotrophic Vibrio sp. isolated from Acropora millepora into conspecific coral larvae. Incorporation of Vibrio sp. cells was observed in coral larvae after 4-h incubation with enriched bacteria. Uptake was restricted to the aboral epidermis of larvae, where Vibrio cells clustered in elongated aggregations. Other bacterial associates were also observed in epidermal areas in FISH analyses. Although the fate and role of these bacteria requires additional investigation, this study describes a powerful approach to further explore cell associations and nutritional pathways in the early life stages of the coral holobiont.

Rhenium and osmium isotopes have been used for decades to date the formation of molybdenite (MoS2), a common mineral in ore deposits and the world’s main source of molybdenum and rhenium. Understanding the distribution of parent 187Re and radiogenic daughter 187Os isotopes in molybdenite is critical in interpreting isotopic measurements because it can compromise the accurate determination and interpretation of mineralization ages. In order to resolve the controls on the distribution of these elements, chemical and isotope mapping of MoS2 grains from representative porphyry copper-molybdenum deposits were performed using electron microprobe and nano-scale secondary ion mass spectrometry. Our results show a heterogeneous distribution of 185,187Re and 192Os isotopes in MoS2, and that both 187Re and 187Os isotopes are not decoupled as previously thought. We conclude that Re and Os are structurally bound or present as nanoparticles in or next to molybdenite grains, recording a complex formation history and hindering the use of microbeam techniques for Re-Os molybdenite dating. Our study opens new avenues to explore the effects of isotope nuggeting in geochronometers.

The oldest widely accepted evidence for oxygenic photosynthesis on Earth comes from hydro-carbon biomarkers extracted from 2.7-billion-year-old shales in the Pilbara Craton of Australia, thought to be evidence of eukaryotes and photosynthetic cyanobacteria. This early date has caused controversy because of the long delay between this earliest appearance of oxygen-producing cyanobacteria and the 'great oxidation event' that caused the rise of atmospheric oxygen some 300 million years later. New work by Rasmussen et al. shows that the organic biomarkers are not of Archaean age and must have entered the rocks later, some time after about 2.2 billion years ago. The earliest unambiguous fossil evidence for eukaryotes and cyanobacteria thus reverts to 1.78–1.68 and 2.15 billion years, respectively. The oldest widely accepted evidence for oxygenic photosynthesis comes from hydrocarbon biomarkers extracted from 2.7-billion-year-old shales in the Pilbara Craton, Australia, thought to be evidence of eukaryotes and photosynthetic cyanobacteria. But evidence now shows that the organic biomarkers were not indigenous to the rocks containing them, and must have entered the rocks after ∼2.2 Gyr ago. The earliest unambiguous fossil evidence for eukaryotes and cyanobacteria thus reverts to 1.78–1.68 and 2.15 Gyr, respectively. The evolution of oxygenic photosynthesis had a profound impact on the Earth’s surface chemistry, leading to a sharp rise in atmospheric oxygen between 2.45 and 2.32 billion years (Gyr) ago1,2 and the onset of extreme ice ages3. The oldest widely accepted evidence for oxygenic photosynthesis has come from hydrocarbons extracted from ∼2.7-Gyr-old shales in the Pilbara Craton, Australia, which contain traces of biomarkers (molecular fossils) indicative of eukaryotes and suggestive of oxygen-producing cyanobacteria4,5,6,7. The soluble hydrocarbons were interpreted to be indigenous and syngenetic despite metamorphic alteration and extreme enrichment (10–20‰) of 13C relative to bulk sedimentary organic matter5,8. Here we present micrometre-scale, in situ 13C/12C measurements of pyrobitumen (thermally altered petroleum) and kerogen from these metamorphosed shales, including samples that originally yielded biomarkers. Our results show that both kerogen and pyrobitumen are strongly depleted in 13C, indicating that indigenous petroleum is 10–20‰ lighter than the extracted hydrocarbons5. These results are inconsistent with an indigenous origin for the biomarkers. Whatever their origin, the biomarkers must have entered the rock after peak metamorphism ∼2.2 Gyr ago9 and thus do not provide evidence for the existence of eukaryotes and cyanobacteria in the Archaean eon. The oldest fossil evidence for eukaryotes and cyanobacteria therefore reverts to 1.78–1.68 Gyr ago and ∼2.15 Gyr ago10,11, respectively. Our results eliminate the evidence for oxygenic photosynthesis ∼2.7 Gyr ago and exclude previous biomarker evidence for a long delay (∼300 million years) between the appearance of oxygen-producing cyanobacteria and the rise in atmospheric oxygen 2.45–2.32 Gyr ago1.

This paper reports results of scanning ion probe studies of silicon implantation profiles in source and drain regions of AlGaN/GaN high-electron-mobility transistor (HEMT) heterostructures. It is shown that both the undoped channel length and the transition region between implanted and non- implanted regions become wider with increasing depth in the structure. These results may explain the previously reported existence of resistance associated with the transition region between implanted and non-implanted semiconductor regions in AlGaN/GaN HEMT heterostructures with non-alloyed Si-implanted source and drain ohmic contact regions.

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg2SiO4) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO2 and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D M (M = Ni or Co) for the combined data set can be fitted to the equation: $$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$ with Ea(Ni) = − 284.3 kJ mol−1 and Ea(Co) = − 275.9 kJ mol−1, with an uncertainty of ±10.2 kJ mol−1. This equation fits the data (24 experiments) to ±0.1 in log D M. The dependence of diffusion on $$a_{{{\text{SiO}}_{2} }}$$ is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg1.8Fe0.2SiO4 at 1,300 °C give a slightly small dependence on $$a_{{{\text{SiO}}_{2} }}$$ , with D $$\propto$$ ( $$a_{{{\text{SiO}}_{2} }}^{0.5}$$ ), presumably because the Mg-site vacancies increase with incorporation of Fe3+ in the Fe-bearing olivines. However, the dependence on fO2 is small, with D $$\propto$$ (fO2)0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO2 magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO2 magmas, such as tholeiitic basalts, at equal temperatures and fO2.