Mineral inclusions encapsulated in diamonds are the oldest, deepest, and most pristine samples of Earth's mantle. They provide age and chemical information over a period of 3.5 billion years—a span ...that includes continental crustal growth, atmospheric evolution, and the initiation of plate tectonics. We compiled isotopic and bulk chemical data of silicate and sulfide inclusions and found that a compositional change occurred 3.0 billion years ago (Ga). Before 3.2 Ga, only diamonds with peridotitic compositions formed, whereas after 3.0 Ga, eclogitic diamonds became prevalent. We suggest that this resulted from the capture of eclogite and diamond-forming fluids in subcontinental mantle via subduction and continental collision, marking the onset of the Wilson cycle of plate tectonics.
The redox state of Earth's convecting mantle, masked by the lithospheric plates and basaltic magmatism of plate tectonics, is a key unknown in the evolutionary history of our planet. Here we report ...that large, exceptional gem diamonds like the Cullinan, Constellation, and Koh-i-Noor carry direct evidence of crystallization from a redox-sensitive metallic liquid phase in the deep mantle. These sublithospheric diamonds contain inclusions of solidified iron-nickel-carbon-sulfur melt, accompanied by a thin fluid layer of methane ± hydrogen, and sometimes majoritic garnet or former calcium silicate perovskite.The metal-dominated mineral assemblages and reduced volatiles in large gem diamonds indicate formation under metalsaturated conditions. We verify previous predictions that Earth has highly reducing deep mantle regions capable of precipitating a metallic iron phase that contains dissolved carbon and hydrogen.
Geological pathways for the recycling of Earth's surface materials into the mantle are both driven and obscured by plate tectonics
. Gauging the extent of this recycling is difficult because ...subducted crustal components are often released at relatively shallow depths, below arc volcanoes
. The conspicuous existence of blue boron-bearing diamonds (type IIb)
reveals that boron, an element abundant in the continental and oceanic crust, is present in certain diamond-forming fluids at mantle depths. However, both the provenance of the boron and the geological setting of diamond crystallization were unknown. Here we show that boron-bearing diamonds carry previously unrecognized mineral assemblages whose high-pressure precursors were stable in metamorphosed oceanic lithospheric slabs at depths reaching the lower mantle. We propose that some of the boron in seawater-serpentinized oceanic lithosphere is subducted into the deep mantle, where it is released with hydrous fluids that enable diamond growth
. Type IIb diamonds are thus among the deepest diamonds ever found and indicate a viable pathway for the deep-mantle recycling of crustal elements.
We perform a set of experiments on photoheating in a water droplet containing gold nanoparticles (NPs). Using photocalorimetric methods, we determine efficiency of light-to-heat conversion (η) which ...turns out to be remarkably close to 1, (0.97 < η < 1.03). Detailed studies reveal a complex character of heat transfer in an optically stimulated droplet. The main mechanism of equilibration is due to convectional flow. Theoretical modeling is performed to describe thermal effects at both nano- and millimeter scales. Theory shows that the collective photoheating is the main mechanism. For a large concentration of NPs and small laser intensity, an averaged temperature increase (at the millimeter scale) is significant (∼7 °C), whereas on the nanometer scale the temperature increase at the surface of a single NP is small (∼0.02 °C). In the opposite regime, that is, a small NP concentration and intense laser irradiation, we find an opposite picture: a temperature increase at the millimeter scale is small (∼0.1 °C) but a local, nanoscale temperature has strong local spikes at the surfaces of NPs (∼3 °C). These studies are crucial for the understanding of photothermal effects in NPs and for their potential and current applications in nano- and biotechnologies.
Single-particle spectroscopy is central to the characterization of plasmonic nanostructures and understanding of light–matter interactions in chiral nanosystems. Although chiral plasmonic ...nanostructures are generally characterized by their circular differential extinction and scattering, single-particle absorption studies can extend our understanding of light–matter interactions. Here, we introduce an experimental observation of photothermal chirality which originated from circular differential absorption of chiral plasmonic nanostructures. Using luminescence ratio thermometry, we identify the optical and photothermal handedness and an absolute temperature difference of 6 K under the right and left circularly polarized light. We observe a circular differential extinction parameter (g ext) of −0.13 in colloidally prepared gold helicoids and compare our findings with numerical simulations using finite element methods. The simulated data showed that circular differential absorption and the maximum temperature of a small cluster of helical nanoparticles are polarization-dependent. We observed an intensity-dependent photothermal g-factor from chiral helicoids that decreases slightly at higher temperatures. We also measure a range of optical g-factors from several gold helicoids, which are attributed to the heterogeneity of helicoids in nanoparticles during synthesis. The principles of differential photothermal response of chiral nanomaterials and heat generation described here can be potentially used for thermal photocatalysis, energy conversion, and electronic applications.
The primary aim of this study was to evaluate the antitumor efficacy of the bromodomain inhibitor JQ1 in pancreatic ductal adenocarcinoma (PDAC) patient-derived xenograft (tumorgraft) models. A ...secondary aim of the study was to evaluate whether JQ1 decreases expression of the oncogene c-Myc in PDAC tumors, as has been reported for other tumor types. We used five PDAC tumorgraft models that retain specific characteristics of tumors of origin to evaluate the antitumor efficacy of JQ1. Tumor-bearing mice were treated with JQ1 (50 mg/kg daily for 21 or 28 days). Expression analyses were performed with tumors harvested from host mice after treatment with JQ1 or vehicle control. An nCounter PanCancer Pathways Panel (NanoString Technologies) of 230 cancer-related genes was used to identify gene products affected by JQ1. Quantitative RT-PCR, immunohistochemistry and immunoblots were carried out to confirm that changes in RNA expression reflected changes in protein expression. JQ1 inhibited the growth of all five tumorgraft models (P<0.05), each of which harbors a KRAS mutation; but induced no consistent change in expression of c-Myc protein. Expression profiling identified CDC25B, a regulator of cell cycle progression, as one of the three RNA species (TIMP3, LMO2 and CDC25B) downregulated by JQ1 (P<0.05). Inhibition of tumor progression was more closely related to decreased expression of nuclear CDC25B than to changes in c-Myc expression. JQ1 and other agents that inhibit the function of proteins with bromodomains merit further investigation for treating PDAC tumors. Work is ongoing in our laboratory to identify effective drug combinations that include JQ1.
A combination of experimental and computational studies have identified a C=O⋅⋅⋅isothiouronium interaction as key to efficient enantiodiscrimination in the kinetic resolution of tertiary heterocyclic ...alcohols bearing up to three potential recognition motifs at the stereogenic tertiary carbinol center. This discrimination was exploited in the isothiourea‐catalyzed acylative kinetic resolution of tertiary heterocyclic alcohols (38 examples, s factors up to >200). The reaction proceeds at low catalyst loadings (generally 1 mol %) with either isobutyric or acetic anhydride as the acylating agent under mild conditions.
Test your resolve: Experimental and computational studies have identified a C=O⋅⋅⋅isothiouronium interaction as key to efficient enantiodiscrimination in the kinetic resolution of tertiary heterocyclic alcohols with up to three potential recognition motifs at the stereogenic tertiary carbinol center. The kinetic resolution of a range of such alcohols was achieved with an isothiourea catalyst and either isobutyric or acetic anhydride.
Indoor residual spraying (IRS) is an important part of malaria control. There is a growing list of insecticide classes; pyrethroids remain the principal insecticide used in bednets but recently, ...novel non-pyrethroid IRS products, with contrasting impacts, have been introduced. There is an urgent need to better assess product efficacy to help decision makers choose effective and relevant tools for mosquito control. Here we use experimental hut trial data to characterise the entomological efficacy of widely-used, novel IRS insecticides. We quantify their impact against pyrethroid-resistant mosquitoes and use a Plasmodium falciparum transmission model to predict the public health impact of different IRS insecticides. We report that long-lasting IRS formulations substantially reduce malaria, though their benefit over cheaper, shorter-lived formulations depends on local factors including bednet use, seasonality, endemicity and pyrethroid resistance status of local mosquito populations. We provide a framework to help decision makers evaluate IRS product effectiveness.
Vision is an important source of information about other minds for sighted children, especially prior to the onset of language. Visually observed actions, eye gaze, and facial expressions of others ...provide information about mental states, such as beliefs, desires, and emotions. Does such experience contribute causally to the development of cortical networks supporting social cognition? To address this question we compared functional development of brain regions supporting theory of mind (ToM), as well as behavioral ToM reasoning, across congenitally blind (n=17) and sighted (n=114) children and adolescents (4–17 years old). We find that blind children in this age range show slightly lower ToM behavioral performance relative to sighted children. Likewise, the functional profile of ToM brain regions is qualitatively similar, but quantitatively weaker in blind relative to sighted children. Alongside prior research, these data suggest that vision facilitates, but is not necessary for, ToM development.
A temperature-dependent photoluminescent thin film of Al0.94Ga0.06N doped with Er3+ is used to measure the temperature of lithographically prepared gold nanodots. The gold nanodots and thin film are ...excited simultaneously with a continuous wave (CW) Nd:YAG 532 nm laser. The gold nanodot is submersed under water, and the dot is subsequently heated. The water immediately surrounding the nanodot is superheated beyond the boiling point up to the spinodal decomposition temperature at 594 ± 17 K. The spinodal decomposition has been confirmed with the observation of critical opalescence. We characterize the laser scattering that occurs in unison with spinodal decomposition due to an increased coherence length associated with the liquid–liquid transition.
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