Role of Polarons in Single-Atom Catalysts: Case Study of Me1 [Au1, Pt1, and Rh1] on TiO2(110)

The local environment of metal-oxide supported single-atom catalysts plays a decisive role in the surface reactivity and related catalytic properties. The study of such systems is complicated by the presence of point defects on the surface, which are often associated with the localization of excess charge in the form of polarons. This can affect the stability, the electronic configuration, and the local geometry of the adsorbed adatoms. In this work, through the use of density functional theory and surface-sensitive experiments, we study the adsorption of Rh-1, Pt-1, and Au-1 metals on the reduced TiO2(110) surface, a prototypical polaronic material. A systematic analysis of the adsorption configurations and oxidation states of the adsorbed metals reveals different types of couplings between adsorbates and polarons. As confirmed by scanning tunneling microscopy measurements, the favored Pt-1 and Au-1 adsorption at oxygen vacancy sites is associated with a strong electronic charge transfer from polaronic states to adatom orbitals, which results in a reduction of the adsorbed metal. In contrast, the Rh-1 adatoms interact weakly with the excess charge, which leaves the polarons largely unaffected. Our results show that an accurate understanding of the properties of single-atom catalysts on oxide surfaces requires a careful account of the interplay between adatoms, vacancy sites, and polarons

Surface chemistry on a polarizable surface: Coupling of CO with KTaO3(001)

Polarizable materials attract attention in catalysis because they have a free parameter for tuning chemical reactivity. Their surfaces entangle the dielectric polarization with surface polarity, excess charge, and orbital hybridization. How this affects individual adsorbed molecules is shown for the incipient ferroelectric perovskite KTaO3. This intrinsically polar material cleaves along (001) into KO- and TaO2-terminated surface domains. At TaO2 terraces, the polarity-compensating excess electrons form a two-dimensional electron gas and can also localize by coupling to ferroelectric distortions. TaO2 terraces host two distinct types of CO molecules, adsorbed at equivalent lattice sites but charged differently as seen in atomic force microscopy/scanning tunneling microscopy. Temperature-programmed desorption shows substantially stronger binding of the charged CO; in density functional theory calculations, the excess charge favors a bipolaronic configuration coupled to the CO. These results pinpoint how adsorption states couple to ferroelectric polarization

IrO2 Surface Complexions Identified Through Machine Learning and Surface Investigations

A Gaussian Approximation Potential (GAP) was trained using density-functional theory data to enable a global geometry optimization of low-index rutile IrO2 facets through simulated annealing. Ab initio thermodynamics identifies (101) and (111) (1x1)-terminations competitive with (110) in reducing environments. Experiments on single crystals find that (101) facets dominate, and exhibit the theoretically predicted (1x1) periodicity and X-ray photoelectron spectroscopy (XPS) core level shifts. The obtained structures are analogous to the complexions discussed in the context of ceramic battery materials.Comment: 13 pages 2 figure

Future constraints on angle-dependent non-Gaussianity from large radio surveys

We investigate how well future large-scale radio surveys could measure different shapes of primordial non-Gaussianity; in particular we focus on angle-dependent non-Gaussianity arising from primordial anisotropic sources, whose bispectrum has an angle dependence between the three wavevectors that is characterized by Legendre polynomials P and expansion coefficients c. We provide forecasts for measurements of galaxy power spectrum, finding that Large-Scale Structure (LSS) data could allow measurements of primordial non-Gaussianity that would be competitive with, or improve upon, current constraints set by CMB experiments, for all the shapes considered. We argue that the best constraints will come from the possibility to assign redshift information to radio galaxy surveys, and investigate a few possible scenarios for the EMU and SKA surveys. A realistic (futuristic) modeling could provide constraints of f≈1(0.5) for the local shape, f of O(10)(O(1)) for the orthogonal, equilateral and folded shapes, and c≈80(2), c≈400(10) for angle-dependent non-Gaussianity showing that only futuristic galaxy surveys will be able to set strong constraints on these models. Nevertheless, the more futuristic forecasts show the potential of LSS analyses to considerably improve current constraints on non-Gaussianity, and so on models of the primordial Universe. Finally, we find the minimum requirements that would be needed to reach σ(c)=10, which can be considered as a typical (lower) value predicted by some (inflationary) models

Repositioning: the fast track to new anti-malarial medicines?

Repositioning of existing drugs has been suggested as a fast track for developing new anti-malarial agents. The compound libraries of GlaxoSmithKline (GSK), Pfizer and AstraZeneca (AZ) comprising drugs that have undergone clinical studies in other therapeutic areas, but not achieved approval, and a set of US Food and Drug Administration (FDA)-approved drugs and other bio-actives were tested against Plasmodium falciparum blood stages. Repositioning of existing therapeutics in malaria is an attractive proposal. Compounds active in vitro at muM concentrations were identified. However, therapeutic concentrations may not be effectively achieved in mice or humans because of poor bio-availability and/or safety concerns. Stringent safety requirements for anti-malarial drugs, given their widespread use in children, make this a challenging area in which to reposition therapy.This work was supported by the Medicines Malaria Venture, St Jude Children's Research Hospital, GlaxoSmithKline Plc and Pfizer Inc

Demonstration of a Hybrid Space Architecture During RIMPAC 2020

The Micro-Satellite Military Utility (MSMU) Project Arrangement (PA) is an agreement under the Responsive Space Capabilities (RSC) Memorandum of Understanding (MOU) that involves the Departments and Ministries of Defence of Australia, Canada, Germany, Italy, the Netherlands, New Zealand, Norway, United Kingdom and United States. MSMU’s charter is to inform a space enterprise that provides military users with reliable access to a broad spectrum of information in an opportunistic environment. Research and Development teams from MSMU partner nations supported Exercise Rim of the Pacific (RIMPAC) 2020 which took place 17 to 31 August 2020 in the Hawaiian region. RIMPAC 2020 provided an opportunity to explore the military utility of a Hybrid Space Architecture (HSA) of satellites including traditional government and commercial satellites, as well as micro-satellites and nanosatellites, by leveraging contributions across the MSMU partner nations. The objective was to continue testing the hypothesis that an HSA, mostly composed of small satellites, can bring significant value to the operational theatre. The MSMU PA partner nations have leveraged several multi-national exercises, with the first being the Exercise RIMPAC 2018. Previous exercises enabled multinational technology advancements, interoperability testing, process refinement, and capability developments to make advancements towards MSMU’s goal to address the warfighter’s need for diverse ISR capabilities. The most recent accomplishment was a major integration effort across mission planning tools, space-based Intelligence, Surveillance and Reconnaissance (ISR) data providers, and exploitation tools. The MSMU team accessed ~256 space-based sensors (EO – Electro Optical, SAR – Synthetic Aperture Radar, AIS – Automatic Identification System) to collect maritime domain and ISR data over a harbor, airfields and open sea. Data was exploited via international channels in order to determine the success rate of capturing pertinent data to be later exploited and disseminated. This paper describes results from the experiment and offers insights into the HSA military utility

A new schedule of fotemustine in temozolomide-pretreated patients with relapsing glioblastoma

In the present study we investigated the feasibility and effectiveness of a new biweekly schedule of fotemustine (FTM) in patients with recurrent glioblastoma, after at least one previous treatment. The primary endpoint was progression-free survival at 6 months; secondary objectives were clinical response, overall survival, disease-free survival, and toxicity. Forty patients (median age 52.8 years; median Karnofsky Performance Status at progression 90) underwent second-line chemotherapy with FTM. Selected patients were previously treated with a standard radiotherapy course with concomitant temozolomide (TMZ). After tumor relapse or progression proven by magnetic resonance imaging (MRI), all patients underwent chemotherapy with FTM, given intravenously at dose of 80 mg/m2 every 2 weeks for five consecutive administrations (induction phase), and then every 3 weeks at 100 mg/m2 as maintenance. A total of 329 infusions were administered; the median number of cycles administered was 8. All patients completed the induction phase, and 29 patients received at least one maintenance infusion. Response to treatment was assessed using MacDonald criteria. One complete response [2.5%, 95% confidence interval (CI): 0–10%], 9 partial responses (22.5%, 95% CI: 15–37%), and 16 stable diseases (40%, 95% CI: 32–51%) were observed. Median time to progression was 6.7 months (95% CI: 3.9–9.1 months). Progression-free survival at 6 months was 61%. Median survival from beginning of FTM chemotherapy was 11.1 months. The schedule was generally well tolerated; the main toxicities were hematologic (grade 3 thrombocytopenia in two cases). To the best of our knowledge, this is the first report specifically dealing with the use of a biweekly induction schedule of FTM. The study demonstrates that FTM has therapeutic efficacy as single-drug second-line chemotherapy with a favorable safety profile