Kinetic and economic analysis of reactive capture of dilute carbon dioxide with Grignard reagents

Carbon Dioxide Utilisation (CDU) processes face significant challenges, especially in the energetic cost of carbon capture from flue gas and the uphill energy gradient for CO2 reduction. Both of these stumbling blocks can be addressed by using alkaline earth metal compounds, such as Grignard reagents, as sacrificial capture agents. We have investigated the performance of these reagents in their ability to both capture and activate CO2 directly from dried flue gas (essentially avoiding the costly capture process entirely) at room temperature and ambient pressures with high yield and selectivity. Naturally, to make the process sustainable, these reagents must then be recycled and regenerated. This would potentially be carried out using existing industrial processes and renewable electricity. This offers the possibility of creating a closed loop system whereby alcohols and certain hydrocarbons may be carboxylated with CO2 and renewable electricity to create higher-value products containing captured carbon. A preliminary Techno-Economic Analysis (TEA) of an example looped process has been carried out to identify the electrical and raw material supply demands and hence determine production costs. These have compared broadly favourably with existing market values

Highly Tunable Emission by Halide Engineering in Lead-Free Perovskite-Derivative Nanocrystals: The Cs2SnX6 (X = Cl, Br, Br/I, I) System

Nanocrystals of Cs2SnX6 (X = Cl, Br, Br0.5I0.5, and I) have been prepared by a simple, optimized, hot-injection method, reporting for the first time the synthesis of Cs2SnCl6, Cs2SnBr6, and mixed Cs2Sn(I0.5Br0.5)6 nanocrystalline samples. They all show a cubic crystal structure with a linear scaling of lattice parameter by changing the halide size. The prepared nanocrystals have spherical shape with average size from 3 to 6 nm depending on the nature of the halide and span an emission range from 444 nm (Cs2SnCl6) to 790 nm (Cs2SnI6) with a further modulation provided by mixed Br/I systems

Tailoring the Phase in Nanoscale MoTe2Grown by Barrier-Assisted Chemical Vapor Deposition

We employed chemical vapor deposition (CVD) from powder precursors aiming at large-area growth of molybdenum ditelluride (MoTe2) thin films, with controlled allotropic 2H and 1T′ phases. This major outcome entails tuning the parametric conditions of the precursor fluxes during the deposition. Using a physical barrier, we induce a concentration gradient of the Te precursor, thus enabling the control of the flux fluid dynamics and the formation of a Te-rich or Te-poor environment. As a consequence, the allotropic phase repartition in the films turns out to be determined by the barrier-induced Te concentration, as clearly evidenced by statistical Raman scattering investigations. The effect of the physical barrier is also reflected in the shape of the crystallite population and in their log-normal areal distribution pointing out to a homogeneous nucleation mode of the MoTe2 crystals. Our approach shows the selective allotropic phase control in the barrier-assisted CVD deposition of MoTe2 by adjusting the kinetics of the chemical reaction rather than with the use of growth surfactants

The Mediterranean Sea Regime Shift at the End of the 1980s, and Intriguing Parallelisms with Other European Basins

Background: Regime shifts are abrupt changes encompassing a multitude of physical properties and ecosystem variables, which lead to new regime conditions. Recent investigations focus on the changes in ecosystem diversity and functioning associated to such shifts. Of particular interest, because of the implication on climate drivers, are shifts that occur synchronously in separated basins. Principal Findings: In this work we analyze and review long-term records of Mediterranean ecological and hydro-climate variables and find that all point to a synchronous change in the late 1980s. A quantitative synthesis of the literature (including observed oceanic data, models and satellite analyses) shows that these years mark a major change in Mediterranean hydrographic properties, surface circulation, and deep water convection (the Eastern Mediterranean Transient). We provide novel analyses that link local, regional and basin scale hydrological properties with two major indicators of large scale climate, the North Atlantic Oscillation index and the Northern Hemisphere Temperature index, suggesting that the Mediterranean shift is part of a large scale change in the Northern Hemisphere. We provide a simplified scheme of the different effects of climate vs. temperature on pelagic ecosystems. Conclusions: Our results show that the Mediterranean Sea underwent a major change at the end of the 1980s that encompassed atmospheric, hydrological, and ecological systems, for which it can be considered a regime shift. We further provide evidence that the local hydrography is linked to the larger scale, northern hemisphere climate. These results suggest that the shifts that affected the North, Baltic, Black and Mediterranean (this work) Seas at the end of the 1980s, that have been so far only partly associated, are likely linked as part a northern hemisphere change. These findings bear wide implications for the development of climate change scenarios, as synchronous shifts may provide the key for distinguishing local (i.e., basin) anthropogenic drivers, such as eutrophication or fishing, from larger scale (hemispheric) climate drivers

Changes in the Phase of the Annual Cycle of Surface Temperature

The annual cycle in the Earth's surface temperature is extremely large—comparable in magnitude to the glacial–interglacial cycles over most of the planet. Trends in the phase and the amplitude of the annual cycle have been observed, but the causes and significance of these changes remain poorly understood—in part because we lack an understanding of the natural variability. Here we show that the phase of the annual cycle of surface temperature over extratropical land shifted towards earlier seasons by 1.7 days between 1954 and 2007; this change is highly anomalous with respect to earlier variations, which we interpret as being indicative of the natural range. Significant changes in the amplitude of the annual cycle are also observed between 1954 and 2007. These shifts in the annual cycles appear to be related, in part, to changes in the northern annular mode of climate variability, although the land phase shift is significantly larger than that predicted by trends in the northern annular mode alone. Few of the climate models presented by the Intergovernmental Panel on Climate Change reproduce the observed decrease in amplitude and none reproduce the shift towards earlier seasons.Earth and Planetary Science

Rational Design of Allosteric and Selective Inhibitors of the Molecular Chaperone TRAP1

The molecular chaperone TRAP1 regulates energy metabolism, and its activity is relevant in cancer and degenerative diseases. Here, Sanchez-Martin et al. identify highly selective allosteric inhibitors of TRAP1. These compounds revert biochemical and pro-neoplastic effects of TRAP1 and could both enlighten its mode of action and disclose novel therapeutic strategies

Home-Based Intervention Tool for Cardiac Telerehabilitation: Protocol for a Controlled Trial

Background: Among cardiovascular diseases, adult patients with congenital heart disease represent a population that has been continuously increasing, which is mainly due to improvement of the pathophysiological framing, including the development of surgical and reanimation techniques. However, approximately 20% of these patients will require surgery in adulthood and 40% of these cases will necessitate reintervention for residual defects or sequelae of childhood surgery. In this field, cardiac rehabilitation (CR) in the postsurgical phase has an important impact on the patient by improving psychophysical and clinical recovery in reducing fatigue and dyspnea to ultimately increase survival. In this context, compliance with the rehabilitation program is a key element for the therapeutic benefits of the program. The increase of mobile health care devices and software has greatly extended self-care capabilities across the spectrum of health care activities. Moreover, the possibility of telemonitoring the progress of this self-care provides elements of empowerment and awareness of one's state of health. As a branch of telehealth, CR can be optimized and facilitated using remote telemedicine devices. Objective: The principal goal of the Innovation in Postoperative Rehabilitation Training and Monitoring (IPOTERI) study is to design, realize, and test a composite and integrated system for postsurgical rehabilitation therapies at home specialized for cardiac surgery. The secondary aims are to implement the system in a "real-life" context of postcardiac surgical rehabilitation, and to create a data set and a data collection methodology to prototype data analytics algorithms and artificial intelligence techniques for customizing the rehabilitation pathway. Methods: The IPOTERI method consists of a telemonitoring platform that guarantees continuity of postoperative care, an intelligent home station based on an Android app for the patient with a user-friendly interface to record vital signals (electrocardiogram, blood pressure, oxygen saturation, and body weight) and access the planning of rehabilitation activities, and a decision support system that communicates with hospital medical records to transmit alerts and specific support information for the formulation and updating of the treatment and care plan. Results: The pilot test started in June 2023 (protocol number 20406/2021) including 50 patients who will be monitored for 12-14 weeks using the developed platform, as described in the Procedures subsection of the Methods section. Conclusions: The IPOTERI approach, based on the processing of data recorded during the monitoring of telemedicine devices used at home during the postsurgical rehabilitation of a cardiac patient, together with clinical data from the perioperative and postoperative periods could have positive effects on adherence to the rehabilitation program and clinical improvement as well as result in overall improvement of quality of life. International registered report identifier (irrid): DERR1-10.2196/47951

Upgraded Pulsating Heat Pipe Only For Space (U-Phos): Results of the 22nd Rexus Sounding Rocket Campaign

A large tube may still behave, to a certain extent, as a capillary in a micro-gravity environment. This very basic concept is here applied to a two-phase passive heat transfer devices in order to obtain a new family of hybrid wickless heat pipes. Indeed, a Loop Thermosyphon, which usually consists of a large tube, closed end to end in a loop, evacuated and partially filled with a working fluid and intrinsically gravity assisted, may become a capillary tube in space condition and turn its thermo-fluidic behavior into a so called Pulsating Heat Pipe (PHP), or better, a Space Pulsating Heat Pipe (SPHP). Since the objective of the present work is to experimentally demonstrate the feasibility of such a hybrid device, a SPHP has been designed, built, instrumented and tested both on ground and microgravity conditions on the 22nd ESA REXUS Sounding Rocket Campaign. Ground tests demonstrate that the device effectively work as a gravity assisted loop thermosyphon, whether the sounding rocket data clearly reveal a change in the thermal hydraulic behavior very similar to the PHP. Since a microgravity period of approximately 120s is not sufficient to reach a pseudo steady state regime, further investigation on a longer term weightless condition is mandatory

U-PHOS Project: Development of a Large Diameter Pulsating Heat Pipe Experiment on board REXUS 22

U-PHOS Project aims to analyse and characterise the behaviour of a large diameter Pulsating Heat Pipe (PHP) on board REXUS 22 sounding rocket. A PHP is a passive thermal control device consisting of a serpentine capillary tube, evacuated, partially filled with a working fluid and finally sealed. In this configuration, the liquid and vapour phases are randomly distributed in the form of liquid slugs and vapour plugs. The heat is efficiently transported by means of the self-sustained oscillatory fluid motion driven by the phase change phenomena. On ground conditions, a small diameter is required in order to obtain a confined slug flow regime. In milli-gravity conditions, buoyancy forces become less intense and the PHP diameter may be increased still maintaining the slug/plug flow configuration typical of the PHP operation. Consequently, the PHP heat power capability may be increased too. U-PHOS aims at proving that a Large Diameter PHP effectively works in milli-g conditions by characterizing its thermal response during a sounding rocket flight. The actual PHP tube is made of aluminum (3 mm inner diameter, filled with FC-72), heated at the evaporator by a compact electrical resistance, cooled at the condenser by a Phase Change Material (PCM) embedded in a metallic foam. The tube wall temperatures are recorded by means of Fibre Bragg Grating (FBG) sensors; the local fluid pressure is acquired by means of a pressure transducer. The present work intends to report the actual status of the project, focusing in particular on the experiment improvements with respect to the previous campaign

BCR-ABL-specific cytotoxic T cells in the bone marrow of patients with Ph(+) acute lymphoblastic leukemia during second-generation tyrosine-kinase inhibitor therapy.

BCR-ABL-specific cytotoxic T cells in the bone marrow of patients with Ph+ acute lymphoblastic leukemia during second-generation tyrosine-kinase inhibitor therap