Two-Dimensional Hydrodynamics of Pre-Core Collapse: Oxygen Shell Burning

By direct hydrodynamic simulation, using the Piecewise Parabolic Method (PPM) code PROMETHEUS, we study the properties of a convective oxygen burning shell in a SN 1987A progenitor star prior to collapse. The convection is too heterogeneous and dynamic to be well approximated by one-dimensional diffusion-like algorithms which have previously been used for this epoch. Qualitatively new phenomena are seen. The simulations are two-dimensional, with good resolution in radius and angle, and use a large (90-degree) slice centered at the equator. The microphysics and the initial model were carefully treated. Many of the qualitative features of previous multi-dimensional simulations of convection are seen, including large kinetic and acoustic energy fluxes, which are not accounted for by mixing length theory. Small but significant amounts of carbon-12 are mixed non-uniformly into the oxygen burning convection zone, resulting in hot spots of nuclear energy production which are more than an order of magnitude more energetic than the oxygen flame itself. Density perturbations (up to 8%) occur at the `edges' of the convective zone and are the result of gravity waves generated by interaction of penetrating flows into the stable region. Perturbations of temperature and electron fraction at the base of the convective zone are of sufficient magnitude to create angular inhomogeneities in explosive nucleosynthesis products, and need to be included in quantitative estimates of yields. Combined with the plume-like velocity structure arising from convection, the perturbations will contribute to the mixing of nickel-56 throughout supernovae envelopes. Runs of different resolution, and angular extent, were performed to test the robustness of theseComment: For mpeg movies of these simulations, see http://www.astrophysics.arizona.edu/movies.html Submitted to the Astrophysical Journa

Numerical Simulations of Penetration and Overshoot in the Sun

We present numerical simulations of convective overshoot in a two-dimensional model of the solar equatorial plane. The simulated domain extends from 0.001 R_sun to 0.93 R_sun, spanning both convective and radiative regions. We show that convective penetration leads to a slightly extended, mildly subadiabatic temperature gradient beneath the convection zone below which there is a rapid transition to a strongly subadiabatic region. A slightly higher temperature is maintained in the overshoot region by adiabatic heating from overshooting plumes. This enhanced temperature may partially account for the sound speed discrepancy between the standard solar model and helioseismology. Simulations conducted with tracer particles suggest that a fully mixed region exists down to at least 0.687 R_sun.Comment: 24 pages, 8 figures, submitted to Ap

Analysis of the shearing instability in nonlinear convection and magnetoconvection

Numerical experiments on two-dimensional convection with or without a vertical magnetic field reveal a bewildering variety of periodic and aperiodic oscillations. Steady rolls can develop a shearing instability, in which rolls turning over in one direction grow at the expense of rolls turning over in the other, resulting in a net shear across the layer. As the temperature difference across the fluid is increased, two-dimensional pulsating waves occur, in which the direction of shear alternates. We analyse the nonlinear dynamics of this behaviour by first constructing appropriate low-order sets of ordinary differential equations, which show the same behaviour, and then analysing the global bifurcations that lead to these oscillations by constructing one-dimensional return maps. We compare the behaviour of the partial differential equations, the models and the maps in systematic two-parameter studies of both the magnetic and the non-magnetic cases, emphasising how the symmetries of periodic solutions change as a result of global bifurcations. Much of the interesting behaviour is associated with a discontinuous change in the leading direction of a fixed point at a global bifurcation; this change occurs when the magnetic field is introduced

Effect of the aniline fragment in Pt(II) and Pt(IV) complexes as anti-proliferative agents. Standard reduction potential as a more reliable parameter for Pt(IV) compounds than peak reduction potential

The problems of resistance and side effects associated with cisplatin and other chemotherapeutic drugs have boosted research aimed at finding new compounds with improved properties. The use of platinum(IV) prodrugs is one alternative, although there is some controversy regarding the predictive ability of the peak reduction potentials. In the work described here a series of fourteen chloride Pt(II) and Pt(IV) compounds was synthesised and fully characterised. The compounds contain different bidentate arylazole heterocyclic ligands. Their cytotoxic properties against human lung carcinoma (A549), human breast carcinoma (MCF7) and human colon carcinoma (HCT116 and HT29) cell lines were studied. A clear relationship between the type of ligand and the anti-proliferative properties was found, with the best results obtained for the Pt(II) compound that contains an aniline fragment, (13), thus evidencing a positive effect of the NH2 group. Stability and aquation studies in DMSO, DMF and DMSO/water mixtures were carried out on the active complexes and an in-depth analysis of the two aquation processes, including DFT analysis, of 13 was undertaken. It was verified that DNA was the target and that cell death occurred by apoptosis in the case of 13. Furthermore, the cytotoxic derivatives did not exhibit haemolytic activity. The reduction of the Pt(IV) compounds whose Pt(II) congeners were active was studied by several techniques. It was concluded that the peak reduction potential was not useful to predict the ability for reduction. However, a correlation between the cytotoxic activity and the standard reduction potential was found.This work has been funded by the Spanish Ministerio de Ciencia, Innovación y Universidades (MCIU), Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER) (RTI2018-100709-B-C21 to BRM, RTI2018-100709-B-C22 to AM, RTI2018-094093-B-I00 to RSP), Junta de Comunidades de Castilla-La Mancha-FEDER (JCCM) (grant SBPLY/19/180501/000260 to BRM), Ministerio de Economía y Competitividad (Project PID2019-104381GB-I00 to GC), Fundación Leticia Castillejo Castillo to MJRH, Junta de Castilla y León, Consejería de Educación y Cultura y Fondo Social Europeo (Projects BU263P18 and BU087G19 to JVC) as well as UCLM-FEDER (grants 2019-GRIN-27183 and 2019-GRIN-27209 to BRM) and University of Girona (MPCUdG2016/076 to AM)

Somatostatin subtype-2 receptor-targeted metal-based anticancer complexes

Conjugates of a dicarba analogue of octreotide, a potent somatostatin agonist whose receptors are overexpressed on tumor cells, with [PtCl 2(dap)] (dap = 1-(carboxylic acid)-1,2-diaminoethane) (3), [(η 6-bip)Os(4-CO 2-pico)Cl] (bip = biphenyl, pico = picolinate) (4), [(η 6-p-cym)RuCl(dap)] + (p-cym = p-cymene) (5), and [(η 6-p-cym)RuCl(imidazole-CO 2H)(PPh 3)] + (6), were synthesized by using a solid-phase approach. Conjugates 3-5 readily underwent hydrolysis and DNA binding, whereas conjugate 6 was inert to ligand substitution. NMR spectroscopy and molecular dynamics calculations showed that conjugate formation does not perturb the overall peptide structure. Only 6 exhibited antiproliferative activity in human tumor cells (IC 50 = 63 ± 2 μ in MCF-7 cells and IC 50 = 26 ± 3 μ in DU-145 cells) with active participation of somatostatin receptors in cellular uptake. Similar cytotoxic activity was found in a normal cell line (IC 50 = 45 ± 2.6 μ in CHO cells), which can be attributed to a similar level of expression of somatostatin subtype-2 receptor. These studies provide new insights into the effect of receptor-binding peptide conjugation on the activity of metal-based anticancer drugs, and demonstrate the potential of such hybrid compounds to target tumor cells specifically. © 2012 American Chemical Society

Conjugation of a Ru(II) Arene Complex to Neomycin or to Guanidinoneomycin Leads to Compounds with Differential Cytotoxicities and Accumulation between Cancer and Normal Cells

A straightforward methodology for the synthesis of conjugates between a cytotoxic organometallic ruthenium(II) complex and amino- and guanidinoglycosides, as potential RNA-targeted anticancer compounds, is described. Under microwave irradiation, the imidazole ligand incorporated on the aminoglycoside moiety (neamine or neomycin) was found to replace one triphenylphosphine ligand from the ruthenium precursor [(η6-p-cym)RuCl(PPh3)2]+, allowing the assembly of the target conjugates. The guanidinylated analogue was easily prepared from the neomycin-ruthenium conjugate by reaction with N,N′-di-Boc-N″-triflylguanidine, a powerful guanidinylating reagent that was compatible with the integrity of the metal complex. All conjugates were purified by semipreparative high-performance liquid chromatography (HPLC) and characterized by electrospray ionization (ESI) and matrix-assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) and NMR spectroscopy. The cytotoxicity of the compounds was tested in MCF-7 (breast) and DU-145 (prostate) human cancer cells, as well as in the normal HEK293 (Human Embryonic Kidney) cell line, revealing a dependence on the nature of the glycoside moiety and the type of cell (cancer or healthy). Indeed, the neomycin-ruthenium conjugate (2) displayed moderate antiproliferative activity in both cancer cell lines (IC50 ≈ 80 μM), whereas the neamine conjugate (4) was inactive (IC50 ≈ 200 μM). However, the guanidinylated analogue of the neomycin-ruthenium conjugate (3) required much lower concentrations than the parent conjugate for equal effect (IC50 = 7.17 μM in DU-145 and IC50 = 11.33 μM in MCF-7). Although the same ranking in antiproliferative activity was found in the nontumorigenic cell line (3 2 > 4), IC50 values indicate that aminoglycoside-containing conjugates are about 2-fold more cytotoxic in normal cells (e.g., IC50 = 49.4 μM for 2) than in cancer cells, whereas an opposite tendency was found with the guanidinylated conjugate, since its cytotoxicity in the normal cell line (IC50 = 12.75 μM for 3) was similar or even lower than that found in MCF-7 and DU-145 cancer cell lines, respectively. Cell uptake studies performed by ICP-MS with conjugates 2 and 3 revealed that guanidinylation of the neomycin moiety had a positive effect on accumulation (about 3-fold higher in DU-145 and 4-fold higher in HEK293), which correlates well with the higher antiproliferative activity of 3. Interestingly, despite the slightly higher accumulation in the normal cell than in the cancer cell line (about 1.4-fold), guanidinoneomycin-ruthenium conjugate (3) was more cytotoxic to cancer cells (about 1.8-fold), whereas the opposite tendency applied for neomycin-ruthenium conjugate (2). Such differences in cytotoxic activity and cellular accumulation between cancer and normal cells open the way to the creation of more selective, less toxic anticancer metallodrugs by conjugating cytotoxic metal-based complexes such as ruthenium(II) arene derivatives to guanidinoglycosides

Thermoelectric generator (TEG) technologies and applications

2021 The Author(s). Nowadays humans are facing difficult issues, such as increasing power costs, environmental pollution and global warming. In order to reduce their consequences, scientists are concentrating on improving power generators focused on energy harvesting. Thermoelectric generators (TEGs) have demonstrated their capacity to transform thermal energy directly into electric power through the Seebeck effect. Due to the unique advantages they present, thermoelectric systems have emerged during the last decade as a promising alternative among other technologies for green power production. In this regard, thermoelectric device output prediction is important both for determining the future use of this new technology and for specifying the key design parameters of thermoelectric generators and systems. Moreover, TEGs are environmentally safe, work quietly as they do not include mechanical mechanisms or rotating elements and can be manufactured on a broad variety of substrates such as silicon, polymers and ceramics. In addition, TEGs are position-independent, have a long working life and are ideal for bulk and compact applications. Furthermore, Thermoelectric generators have been found as a viable solution for direct generation of electricity from waste heat in industrial processes. This paper presents in-depth analysis of TEGs, beginning with a comprehensive overview of their working principles such as the Seebeck effect, the Peltier effect, the Thomson effect and Joule heating with their applications, materials used, Figure of Merit, improvement techniques including different thermoelectric material arrangements and technologies used and substrate types. Moreover, performance simulation examples such as COMSOL Multiphysics and ANSYS-Computational Fluid Dynamics are investigated

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries