Formation of the Perovskite Phase in the PbMg1/3Nb2/3O3─PbTiO3 System

The reaction sequences during calcination of oxide mixtures were studied for the PbMg_1/3Nb_2/3O₃─PbTiO₃ (PMN-PT) system. The effect of reactivity and composition of the starting mixtures was investigated. In the present study, a B-site-deficient, cubic pyrochlore phase in the PbO-Nb₂O₅ system was formed at 500°C. The perovskite phase of PMN was formed at 7007deg;C through the diffusion of MgO into the pyrochlore phase. The lattice parameter of the pyrochlore phase decreased as this transformation to perovskite progressed.     

Role of peroxy chemistry in the high-pressure ignition of n-butanol – Experiments and detailed kinetic modelling

Despite considerable interest in butanol as a potential biofuel candidate, its ignition behaviour at elevated pressures still remains largely unexplored. The present study investigates the oxidation of n-butanol in air at pressures near 80 bar. Ignition delays were determined experimentally in the temperature range of 795–1200 K between 61 and 92 bar. The time of ignition was determined by recording pressure and CH-emission time histories throughout the course of the experiments. The results display the first evidence of the influence of negative temperature coefficient (NTC) behaviour which was not observed in earlier ignition studies. The high-pressure measurements show that NTC behaviour is enhanced as pressures are increased. The experimental results were modelled using an improved chemical kinetic mechanism which includes a simplified sub-mechanism for butyl-peroxy formation and isomerisation reactions currently incompletely accounted for in n-butanol kinetic models. The detailed mechanism validated with the high-pressure ignition results for realistic engine in-cylinder conditions can have significant impact on future advanced low-temperature combustion engines.     

Experimental investigation of the swelling/shrinkage of a hydride bed in a cell during hydrogen absorption/desorption cycles

The storage of hydrogen in hydride materials is currently much researched as a mean of energy storage. This reversible storage is achieved by successive hydriding and dehydriding reactions. During these reactions, the material undergoes structural transformations which result in swelling of the hydride powder grains due to the absorption of hydrogen. This phenomenon can generate major mechanical stresses on the cell containing the hydride. The present experimental study examines the cyclic swelling of a granular bed consisting of hydride Ti–Cr–V + Zr–Ni. Two superimposed phenomena are identified: a cyclic rearrangement causing a reduction and then an increase in porosity coupled with gradual densification of the stack.     

Polymeric solar cells based on P3HT:PCBM: Role of the casting solvent

Polymeric photovoltaic (PV) solar cells have been fabricated using six solvents: chloroform (CHCl₃), toluene (T), chlorobenzene (CB), orthodichlorobenzene (ODCB), 1,2,3,4-tetrahydronaphthalene (THN) and 1,2,4-trichlorobenzene (TCB). The active layers were composed of poly(3-hexyl)thiophene (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). Special care has been taken to keep all experimental parameters constant (thickness of the active layers, donor/acceptor weight ratio, area of active surface and electrodes) in order to avoid artefacts and truly study the effect of solvents. Studies using atomic force microscopy (AFM) and optical absorption (UV-vis) showed the relationship between the photovoltaic performance and the evaporation rate of solvents. The use of solvents with high boiling point results in a higher degree of organization in the structure of P3HT. A direct comparison with devices processed with thermal treatment has also been performed. As often reported thermal annealing increases photo-conversion efficiency of devices created from common solvents, due to better separation of phase between the two materials of the blend. In the case of solvents with high boiling point such as THN and TCB, neither phase separation nor modification of P3HT crystallization induced by thermal annealing has been observed. However thermal treatment appears to enhance performance, ensuing the evaporation of remaining solvent in the active layers. An overview of the effect of solvent on the electrical properties of films containing pure P3HT and P3HT:PCBM blend reported in the literature has been completed for the discussion.     

Involvement of GPx-3 in the Reciprocal Control of Redox Metabolism in the Leukemic Niche

The bone marrow (BM) microenvironment plays a crucial role in the development and progression of leukemia (AML). Intracellular reactive oxygen species (ROS) are involved in the regulation of the biology of leukemia-initiating cells, where the antioxidant enzyme GPx-3 could be involved as a determinant of cellular self-renewal. Little is known however about the role of the microenvironment in the control of the oxidative metabolism of AML cells. In the present study, a coculture model of BM mesenchymal stromal cells (MSCs) and AML cells (KG1a cell-line and primary BM blasts) was used to explore this metabolic pathway. MSC-contact, rather than culture with MSC-conditioned medium, decreases ROS levels and inhibits the Nrf-2 pathway through overexpression of GPx3 in AML cells. The decrease of ROS levels also inactivates p38MAPK and reduces the proliferation of AML cells. Conversely, contact with AML cells modifies MSCs in that they display an increased oxidative stress and Nrf-2 activation, together with a concomitant lowered expression of GPx-3. Altogether, these experiments suggest that a reciprocal control of oxidative metabolism is initiated by direct cell–cell contact between MSCs and AML cells. GPx-3 expression appears to play a crucial role in this cross-talk and could be involved in the regulation of leukemogenesis.     

Dichloroacetate Radiosensitizes Hypoxic Breast Cancer Cells

Mitochondrial metabolism is an attractive target for cancer therapy. Reprogramming metabolic pathways can potentially sensitize tumors with limited treatment options, such as triple-negative breast cancer (TNBC), to chemo- and/or radiotherapy. Dichloroacetate (DCA) is a specific inhibitor of the pyruvate dehydrogenase kinase (PDK), which leads to enhanced reactive oxygen species (ROS) production. ROS are the primary effector molecules of radiation and an increase hereof will enhance the radioresponse. In this study, we evaluated the effects of DCA and radiotherapy on two TNBC cell lines, namely EMT6 and 4T1, under aerobic and hypoxic conditions. As expected, DCA treatment decreased phosphorylated pyruvate dehydrogenase (PDH) and lowered both extracellular acidification rate (ECAR) and lactate production. Remarkably, DCA treatment led to a significant increase in ROS production (up to 15-fold) in hypoxic cancer cells but not in aerobic cells. Consistently, DCA radiosensitized hypoxic tumor cells and 3D spheroids while leaving the intrinsic radiosensitivity of the tumor cells unchanged. Our results suggest that although described as an oxidative phosphorylation (OXPHOS)-promoting drug, DCA can also increase hypoxic radioresponses. This study therefore paves the way for the targeting of mitochondrial metabolism of hypoxic cancer cells, in particular to combat radioresistance.