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Creators/Authors contains: "Xu, Man"

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  1. Abstract Fluids and melts in planetary interiors significantly influence geodynamic processes from volcanism to global‐scale differentiation. The roles of these geofluids depend on their viscosities (η). Constraining geofluidηat relevant pressures and temperatures relies on laboratory‐based measurements and is most widely done using Stokes' Law viscometry with falling spheres. Yet small sample chambers required by high‐pressure experiments introduce significant drag on the spheres. Several correction schemes are available for Stokes' Law but there is no consensus on the best scheme(s) for high‐pressure experiments. We completed high‐pressure experiments to test the effects of (a) the relative size of the sphere diameter to the chamber diameter and (b) the top and bottom of the chamber, that is, the ends, on the sphere velocities. We examined the influence of current correction schemes on the estimated viscosity using Monte Carlo simulations. We also compared previous viscometry work on various geofluids in different experimental setups/geometries. We find the common schemes for Stokes' Law produce statistically distinct values ofη. When inertia of the sphere is negligible, the most appropriate scheme may be the Faxén correction for the chamber walls. Correction for drag due to the chamber ends depends on the precision in the sinking distance and may be ineffective with decreasing sphere size. Combining the wall and end corrections may overcorrectη. We also suggest the uncertainty inηis best captured by the correction rather than propagated errors from experimental parameters. We develop an overlying view of Stokes' Law viscometry at high pressures. 
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  2. Deeply subducted carbonates likely cause low-degree melting of the upper mantle and thus play an important role in the deep carbon cycle. However, direct seismic detection of carbonate-induced partial melts in the Earth’s interior is hindered by our poor knowledge on the elastic properties of carbonate melts. Here we report the first experimentally determined sound velocity and density data on dolomite melt up to 5.9 GPa and 2046 K by in-situ ultrasonic and sink-float techniques, respectively, as well as first-principles molecular dynamics simulations of dolomite melt up to 16 GPa and 3000 K. Using our new elasticity data, the calculated V P /V S ratio of the deep upper mantle (∼180–330 km) with a small amount of carbonate-rich melt provides a natural explanation for the elevated V P /V S ratio of the upper mantle from global seismic observations, supporting the pervasive presence of a low-degree carbonate-rich partial melt (∼0.05%) that is consistent with the volatile-induced or redox-regulated initial melting in the upper mantle as argued by petrologic studies. This carbonate-rich partial melt region implies a global average carbon (C) concentration of 80–140 ppm. by weight in the deep upper mantle source region, consistent with the mantle carbon content determined from geochemical studies. 
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  3. Abstract A new [4+2] cycloaddition of allenyne‐alkyne is developed. The reaction is believed to proceed with forming an α,3‐dehydrotoluene intermediate. This species behaves as a σπ‐diradical to react with a hydrogen atom donor, whereas it displays a zwitterionic reactivity toward weak nucleophiles. The efficiency of trapping α,3‐dehydrotoluene depends not only on its substituents but also the trapping agents. Notable features of the reaction are the activating role of the extra alkyne of the 1,3‐diyne that reacts with the allenyne moiety and the opposite mode of trapping with oxygen and nitrogen nucleophiles. Oxygen nucleophiles result in the oxygen‐end incorporation at the benzylic position of the α,3‐dehydrotoluene, whereas with amine nucleophiles the nitrogen‐end is incorporated into the aromatic core. Relying on the allenyne‐alkyne cycloaddition as an enabling strategy, a concise total synthesis of phosphodiesterase‐4 inhibitory selaginpulvilin A is realized. 
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