Repurposing of CO2 to valuable hydrocarbons is crucial for energy security and a balanced carbon cycle. Reverse water gas shift chemical looping (RWGS-CL) is capable of efficient CO2 to CO conversion ...at a low temperature of ∼600 °C with unprecedented rates using the La0.75Sr0.25FeO3 (LSF) perovskite-type oxide amalgamated with silica. The LSF/SiO2 composite (25% LSF by mass) promotes a notable extent of oxygen vacancies in the active phase, a key parameter for CO2 conversion. In each of eight RWGS-CL cycles, CO generation yields of LSF/SiO2 surpass those of LSF alone by about 200%, producing 2.6 mmol of CO gLSF –1 at a peak rate of 0.8 mmol CO gLSF –1 min–1. This significant improvement is concomitant with a decreased average LSF crystallite size retained at these low thermochemical reaction temperatures. Evidence of this enhancement points to perovskite particle size reduction by silica, lattice strain induced by the support, and curtailed quantities of secondary phases that limit accessibility to active surfaces. In this contribution, an appropriate stable platform for improving earth abundancy in perovskite-based redox materials is demonstrated for industrial-scale low-temperature CO2 thermochemical conversion.
Purpose To (1) define the cumulative recurrence rate after primary anterior shoulder dislocation in Level I and II comparative studies and (2) to pool risk ratios for common risk factors to provide a ...clinically practical hierarchy of modifiable and nonmodifiable risk factors for recurrence. Methods Level I and II prognostic studies were identified using the electronic databases CINAHL, Embase, and MEDLINE from inception to December 2014. Included studies (n = 15) had recurrent dislocation as the main outcome, and a minimum 2-year follow-up. The cumulative odds ratio of prognostic factors was calculated where appropriate. Bias was assessed in each study using the Quality in Prognosis Studies (QUIPS) tool. Results The reported rate of recurrence ranged from 19% to 88% (pooled overall = 21%; pooled Level I only = 47%). The pooled time to recurrence was 10.8 months (standard deviation 0.42). Male sex (n = 6 studies) conferred a 2.68 (1.66-4.31; P < .001) and patient age <20 years (n = 4 studies) conferred a 12.76 (5.77-28.2; P < .001; v >20 years) increased odds of recurrence. An associated greater tuberosity fracture (n = 7 studies) decreased the odds of recurrence by 3.8 times (2.94-5.00; P < .001). The quality of evidence was moderate for age, low for sex, and very low for all other prognostic variables. Conclusions The pooled rate of recurrence after primary anterior shoulder instability was found to be 21% among moderate- to high-quality prognostic studies. Male sex and younger age predicted a significantly higher risk of recurrent instability (approaching 80%), whereas concurrent fracture of the greater tuberosity significantly decreased the risk of subsequent recurrent dislocation. However, considering the quality of available evidence for these predictors, there remains a clear need for further high-quality prospective studies. Level of Evidence Level II, systematic review of Level I and II prognostic studies.
Dry reforming catalysts, especially those with activity at moderate temperatures, have been intensely investigated to enhance the conversion of biogas. Here, Ru is evaluated as a promoter for Ni-Mg ...based catalysts. Catalysts based on 1.4 wt%Ni-1.0 wt%Mg-Ce0.6Zr0.4O2 with Ru (0.02–0.32 wt%) were prepared using incipient wetness. The reducibility of the catalysts and conversions increased with increasing Ru content. Increases in conversions with increasing Ru loading was attributed to the additional active sites and synergistic effect between Ru and Ni, which weakened Ni-Mg interactions. Samples showed dry reforming activity at low temperatures (450–510 °C). Reaction rates and activation energies of higher loading Ru samples (1.4 wt%Ni-1.0 wt%Mg/Ce0.6Zr0.4 O2 with 0.16 and 0.32 wt%Ru) decreased when the reduction temperature was raised from 300 to 400 °C. A 20 h TOS study showed stable catalytic activity with minimal coke deposition. The results suggest that Ru is an alternative to Pt in promoting low temperature dry reforming of methane.
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•La0.75Sr0.25FeO3 perovskite oxide combined with various supports and evaluated for thermochemical CO2 conversion.•SiO2 support enhanced CO yield by 150% compared to unsupported ...perovskite after reduction at 600 °C.•Enhancement by silica support caused by restructuring that increased perovskite oxide surface area.•Some support lowered perovskite oxide performance due to overgrowth.
Perovskite-type oxides show clear potential for thermochemical solar-driven CO2 conversion. These materials exhibit the exact characteristics (e.g., structural endurance and high oxygen redox capacity and exchange kinetics) required by the low temperature reverse water-gas shift chemical looping process. In this study, the La0.75Sr0.25FeO3 (LSF) perovskite oxide was combined with various supports, including popular redox materials CeO2 and ZrO2 along with more abundant alternatives such as Al2O3, SiO2, and TiO2, for potential application at industrial scale. Supporting LSF on SiO2 by 25% mass resulted in the largest increase of 150% in CO yields relative to unsupported perovskite after reduction at 600 °C. This is a result of significantly reduced perovskite oxide particle size confirmed by SEM/TEM imaging and crystallite size from Scherrer analyses of XRD patterns. Due to solid-state reactions, minor secondary phases were observed at the LSF:support interface when using SiO2 or TiO2. Oxygen vacancy formation occurred only on the perovskite oxide phase, as suggested by low temperature experiments and consistent with density functional theory calculations. The role of each metal oxide support towards suppressing or enhancing the CO2 conversion is elucidated. Through utilization of SiO2 as support, the reverse water-gas shift chemical looping process using perovskite-based composites was significantly improved.
A massive, irreparable rotator cuff tear may cause significant pain and dysfunction. However, the efficacy of nonoperative treatment modalities in this subset of patients is not currently well known. ...Also, there is currently no gold standard nonoperative protocol to guide treatment. The goal of the present systematic review is to determine if there is any evidence to support the use of various nonoperative treatment modalities and synthesize a standardized nonoperative treatment protocol for the patient with a massive irreparable rotator cuff tear.
A comprehensive review of the literature utilizing PRISMA guidelines was performed. Studies involving clinical outcomes of nonoperative treatment of massive, irreparable rotator cuff tears were included. Articles were reviewed by 2 reviewers to determine inclusion or exclusion based on established criteria. Selected articles were reviewed for results of clinical and functional outcomes. The studies were also reviewed to determine their level of evidence and potential sources of bias. A standardized nonoperative treatment protocol was developed by taking described elements of the protocols used in studies that demonstrated clinical improvement beyond the MCID for the outcome scores used by the authors.
A total of 10 studies met inclusion criteria for our studies. Of the included studies, 1 was Level III evidence and the remaining 9 were Level IV evidence. Multiple studies showed significant improvement exceeding the MCID for functional outcome scores following treatment. Also, several studies demonstrated significant improvements in strength and range of motion. The overall success of nonoperative treatment ranged from 32%-96%. The synthesized nonoperative treatment protocol is characterized by requiring some supervised physical therapy, often requiring 12 weeks or more, focusing on supine exercises with gradual progression to upright. Corticosteroid injections and nonsteroidal anti-inflammatory drugs may also be of benefit.
Despite low-quality evidence, nonoperative treatment has been shown to be efficacious for patients with chronic, massive, irreparable rotator cuff tears. Using these results, a synthesized rehabilitation program was developed to guide clinicians when treating patients with massive irreparable rotator cuff tears.
A selective and stable alumina-supported In-promoted Fe catalyst (10 mol % In based on Fe) was discovered for converting syngas (2:1 H2/CO ratio) to olefins with high selectivity (45% with CO2 ...included) and a remarkable stability (72 h run) at a CO conversion of 10% at 400 °C and 5 bar. The X-ray photoelectron spectroscopy results indicated that incorporating In into Fe catalysts changed the chemical bonding state of Fe and Fe/In composition near the surface layers, which affected the catalytic reactivity. Steady-state isotopic transient kinetic analysis showed that more stable CHx fragments are present on the catalyst surface when incorporating In into Fe, which can promote C–C coupling reaction toward olefins. Our study demonstrates that introducing In into Fe catalysts on Al2O3 support can lower CO activation abilities. It has more impacts on lowering hydrogenation activity, which permits more C–C couplings and like of “ene” hydrogenation. Moreover, weakening CO adsorption both in terms of sites and strength encouraged CO toward hydrocarbons rather than CO2.
Carbon dioxide conversion to carbon monoxide was studied in an intensified chemical looping reverse water–gas shift reaction (RWGS–CL) process using parent perovskite-type oxides as oxygen carriers. ...Five different strontium-doped lanthanum cobaltites, La1–X Sr X CoO3−δ (0 ≤ X ≤1 in steps of 0.25), were synthesized using the Pechini method and their structures were examined with X-ray diffraction (XRD). Temperature-programmed (H2-TPR, CO2-TPO) and isothermal CO2 conversion experiments were performed to evaluate their properties and abilities for carbon dioxide conversion. The production of carbon monoxide from the reduced parent oxides is enhanced when X = 0.25. From the three H2-reduction temperatures studied (400, 500, and 600 °C), 500 °C was determined as the optimum, presumably due to the formation of mixed oxides and metallic cobalt crystalline phases (observed via XRD) in close contact. Furthermore, isothermal CO2 conversion rates increased with temperature over the tested range (650 to 850 °C). Results indicated that perovskite-type oxides can be used as oxygen carriers in a RWGS–CL process where separation of the products is achieved, which facilitates subsequent synthesis of liquid hydrocarbons or methanol. Hydrogen obtained by water splitting or electrolysis would make the process sustainable assuming solar or wind is used to drive the reaction.
Umbralisib (TGR-1202) is a novel next-generation inhibitor of phosphatidylinositol 3-kinase (PI3K) isoform p110δ (PI3Kδ), which is structurally distinct from other PI3Kδ inhibitors and shows improved ...isoform selectivity. Umbralisib also uniquely inhibits casein kinase-1ε, a major regulator of protein translation. The aim of this first-in-human phase 1 study was to establish the safety and preliminary activity profile of umbralisib in patients with haematological malignancies.
We did an open-label, phase 1, dose-escalation study at seven clinics in the USA. We recruited patients aged at least 18 years with relapsed or refractory chronic lymphocytic leukaemia or small lymphocytic lymphoma, B-cell and T-cell non-Hodgkin lymphoma, or Hodgkin's lymphoma, who had received one or more previous lines of therapy, with measurable and assessable disease, and adequate organ system function. Patients self-administered an umbralisib oral tablet once per day in 28-day cycles, with dose escalation done in a traditional 3 + 3 design to establish safety and determine the maximum tolerated dose. In initial cohorts, patients took umbralisib in a fasting state at a starting dose of 50 mg, increasing to 100, 200, 400, 800, 1200, and 1800 mg until the maximum tolerated dose was reached, or the maximal dose cohort was accrued without a dose-limiting toxicity. Subsequent cohorts self-administered a micronised formulation of umbralisib tablet in a fed state at an initial dose of 200 mg, increased in increments to 400, 800, 1200, and 1800 mg until the maximum tolerated dose or the maximal dose level was accrued. In August, 2014, all patients still on study were transitioned to 800 mg of the micronised formulation and dosing of the initial formulation was discontinued. The primary endpoints of the study were investigator-assessed safety in all treated patients (the safety population), the maximum tolerated dose, and the pharmacokinetics of umbralisib. Secondary endpoints included preliminary assessments of anti-cancer activity (objective responses and duration of response). Follow-up stopped for a patient once they discontinued therapy. This study has been completed and is registered with ClinicalTrials.gov, number NCT01767766.
Between Jan 17, 2013, and Jan 14, 2016, we enrolled and treated 90 patients with umbralisib. The median duration of treatment and follow-up was 4·7 cycles (IQR 2·0–14·0) or 133 days (IQR 55–335). The most common treatment-emergent adverse events irrespective of causality were diarrhoea (in 39 43% of 90 patients), nausea (38 42%), and fatigue (28 31%). The most common grade 3 or 4 adverse events were neutropenia (in 12 13% patients), anaemia (eight 9%) and thrombocytopenia (six 7%). Serious adverse events considered at least possibly related to umbralisib occurred in seven patients: pneumonia in three (3%) patients, lung infection in one (1%), febrile neutropenia in one (1%), and colitis in two (2%), one of whom also had febrile neutropenia. The maximum tolerated dose was 1200 mg of the micronised formulation, with 800 mg of this formulation selected as the recommended phase 2 dose. Both cases of colitis occurred at above the recommended phase 2 dose. 33 (37%) of the 90 patients enrolled had an objective response to treatment with umbralisib.
Umbralisib was well tolerated and showed preliminary signs of activity in patients with relapsed or refractory haematological malignancies. The safety profile of umbralisib in this phase 1 study was distinct from that of other PI3Kδ inhibitors, with fewer occurrences of autoimmune-like toxicities such as colitis. These findings warrant further evaluation of this agent in this setting.
TG Therapeutics.
