Machine learning potentials for complex aqueous made

Simulation techniques based on accurate and efficient representations of potential energy surfaces are urgently needed for the understanding of complex systems such as solid–liquid interfaces. Here we present a machine learning framework that enables the efficient development and validation of models for complex aqueous systems. Instead of trying to deliver a globally optimal machine learning potential, we propose to develop models applicable to specific thermodynamic state points in a simple and user-friendly process. After an initial ab initio simulation, a machine learning potential is constructed with minimum human effort through a data-driven active learning protocol. Such models can afterward be applied in exhaustive simulations to provide reliable answers for the scientific question at hand or to systematically explore the thermal performance of ab initio methods. We showcase this methodology on a diverse set of aqueous systems comprising bulk water with different ions in solution, water on a titanium dioxide surface, and water confined in nanotubes and between molybdenum disulfide sheets. Highlighting the accuracy of our approach with respect to the underlying ab initio reference, the resulting models are evaluated in detail with an automated validation protocol that includes structural and dynamical properties and the precision of the force prediction of the models. Finally, we demonstrate the capabilities of our approach for the description of water on the rutile titanium dioxide (110) surface to analyze the structure and mobility of water on this surface. Such machine learning models provide a straightforward and uncomplicated but accurate extension of simulation time and length scales for complex systems

High Resolution Chandra Spectroscopy of Gamma Cassiopeia (B0.5IVe)

gamma Cas has long been famous for its unique hard X-ray characteristics. We report herein on a 53 ks Chandra HETGS observation of this target. An inspection of our spectrum shows that it is quite atypical for a massive star, with abnormally weak Fe XXV, XXVI lines, Ly-alpha lines of H-like species from Fe XVII, XXIII, XXIV, S XVI, Si XIV, Mg XII, Ne X, O VII, VIII, and N VII. Also, line ratios of the rif-triplet of for a few He-like ions XVII are consistent with the dominance of collisional atomic processes. Yet, the presence of Fe and Si fluorescence K features indicates that photoionization also occurs in nearby cold gas. The line profiles indicate a mean velocity at rest and a broadening of 500 km/s. A global fitting analysis of the line and continuum spectrum finds that there are 3-4 plasma emission components. The dominant hot (12 keV) component and has a Fe abundance of 0.22 solar. Some fraction of this component (10-30%) is heavily absorbed. The other 2-3 components, with temperatures 0.1, 0.4, 3 keV, are "warm," have a nearly solar composition, a lower column absorption, and are responsible for most other emission lines. The strength of the fluorescence features and the dual-column absorption model for the hot plasma component suggest the presence near the hot sites of a cold gas structure with a column density of 10^23 cm^-2. Since this value is consistent with theoretical estimates of the vertical disk column of this star, these attributes suggest that the X-rays originate near the star or disk. It is possible that the Fe anomaly in the hot component is related to the First Ionization Potential effect found in coronal structures around active cool stars. This would be yet another indication that the X-rays -rays are produced in the immediate vicinity of the Be star.Comment: 32 pages, 4 figures (Fig. 3 colorized.) To be published in 01/10/04 Astrophysical Journal, Main Journal; included figures and updated formattin

The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes.

Publication status: PublishedThe nature of ion-ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion-ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene's electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.Schmidt Science Fellows, in partnership with the Rhodes Trust; Trinity College, Cambridge; Gates Cambridge Trust; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) project number 500244608; European Research Council advanced fellowship (Grant No. 835073); Royal Society Research Professorship; European Research Council project (Grant No. 101071937

The Interplay of Solvation and Polarization Effects on Ion Pairing in Nanoconfined Electrolytes.

The nature of ion-ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion-ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene's electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.Schmidt Science Fellows, in partnership with the Rhodes Trust; Trinity College, Cambridge; Gates Cambridge Trust; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) project number 500244608; European Research Council advanced fellowship (Grant No. 835073); Royal Society Research Professorship; European Research Council project (Grant No. 101071937

From divergence to convergence: re-evaluating the history behind China’s economic boom

China’s long-term economic dynamics pose a formidable challenge to economic historians. The Qing Empire (1644-1911), the world’s largest national economy prior to the 19th century, experienced a tripling of population during the 17th and 18th centuries with no signs of diminishing per capita income. In some regions, the standard of living may have matched levels recorded in advanced regions of Western Europe. However, with the Industrial Revolution a vast gap emerged between newly rich industrial nations and China’s lagging economy. Only with an unprecedented growth spurt beginning in the late 1970s has the gap separating China from the global leaders been substantially diminished, and China regained its former standing among the world’s largest economies. This essay develops an integrated framework for understanding this entire history, including both the long period of divergence and the more recent convergent trend. The analysis sets out to explain how deeply embedded political and economic institutions that had contributed to a long process of extensive growth subsequently prevented China from capturing the benefits associated with new technologies and information arising from the Industrial Revolution. During the 20th century, the gradual erosion of these historic constraints and of new obstacles created by socialist planning eventually opened the door to China’s current boom. Our analysis links China’s recent economic development to important elements of its past, while using the success of the last three decades to provide fresh perspectives on the critical obstacles undermining earlier modernization efforts, and their removal over the last century and a half

86Y-DOTA0)-D-Phe1-Tyr3-octreotide (SMT487)--a phase 1 clinical study: pharmacokinetics, biodistribution and renal protective effect of different regimens of amino acid co-infusion.

The pharmacokinetics and dosimetry of (86)Y-DOTA(0)- d-Phe(1)-Tyr(3)-octreotide ((86)Y-SMT487) were evaluated in a phase I positron emission tomography (PET) study of 24 patients with somatostatin receptor-positive neuroendocrine tumours. The effect of amino acid (AA) co-infusion on renal and tumour uptake was assessed in a cross-over randomised setting. Five regimens were tested: no infusion, 4-h infusion of 120 g mixed AA (26.4 g l-lysine + l-arginine), 4 h l-lysine (50 g), 10 h 240 g mixed AA (52.8 g l-lysine + l-arginine) and 4 h Lys-Arg (25 g each). Comparisons were performed on an intra-patient basis. Infusions of AA started 0.5 h prior to injection of (86)Y-SMT487 and PET scans were obtained at 4, 24 and 48 h p.i. Absorbed doses to tissues were computed using the MIRD3 method. (86)Y-SMT487 displayed rapid plasma clearance and exclusive renal excretion; uptake was noted in kidneys, tumours, spleen and, to a lesser extent, liver. The 4-h mixed AA co-infusion significantly ( P<0.05) reduced (86)Y-SMT487 renal uptake by a mean of 21%. This protective effect was significant on the dosimetry data (3.3+/-1.3 vs 4.4+/-1.0 mGy/MBq; P<0.05) and was further enhanced upon prolonging the infusion to 10 h (2.1+/-0.4 vs 1.7+/-0.2 mGy/MBq; P<0.05). Infusion of Lys-Arg but not of l-lysine was more effective in reducing renal uptake than mixed AA. Infusion of AA did not result in reduced tumour uptake. The amount of (90)Y-SMT487 (maximum allowed dose: MAD) that would result in a 23-Gy cut-off dose to kidneys was calculated for each study: MAD was higher with mixed AA co-infusion by a mean of 46% (10-114%, P<0.05 vs no infusion). In comparison with 4 h mixed AA, the MAD was higher by a mean of 23% (9-37%; P<0.05) with prolonged infusion and by a mean of 16% (2-28%; P<0.05) with Lys-Arg. We conclude that infusion of large amounts of AA reduces renal exposure during peptide-based radiotherapy and allows higher absorbed doses to tumours. The prolongation of the infusion from 4 to 10 h further enhances the protective effect on the kidneys