Search results for "Redox"
showing 10 items of 619 documents
Dicopper(II) Metallacyclophanes with Electroswitchable Polymethyl-Substitutedpara-Phenylene Spacers
2013
Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2]4- have been prepared by the CuII-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N′-para- phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N′-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N′-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation w…
Tuning the electronic properties and the planarity degree in the π-extended TTF series: the prominent role of heteroatoms
2018
The main asset of small molecules for application in organic electronics lies in the tunability of their electronic properties owing to the precise control of their molecular design. Semiconducting properties in organic compounds are for instance closely linked to the molecular planarity degree, including when considering various redox states. Among those species, the π-extended TTF (exTTF: 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene) presents fascinating redox and structural properties, which have been extensively studied in various fields of organic electronics. Here we show that S-exTTF, a sulfur enriched π-isoelectronic dithieno analogue of pristine exTTF, synthesized through…
Direct measurement of the melting temperature of supported DNA by electrochemical method
2003
The development of biosensors based on DNA hybridization requires a more precise knowledge of the thermodynamics of the hybridization at a solid interface. In particular, the selectivity of hybridization can be affected by a lot of parameters such as the single-strand (ss)DNA density, the pH, the ionic strength or the temperature. The melting temperature, T(m), is in part a function of the ionic strength and of the temperature and therefore provides a useful variable in the control of the selectivity and sensitivity of a DNA chip. The electrochemical technique has been used to determine the T(m) values when the probe is tethered by a DNA self-assembled monolayer (SAM). We have built a speci…
The significance of the order of impregnation on the activity of vanadia promoted palladium-alumina catalysts for propane total oxidation
2011
The increased activity of alumina-supported palladium catalysts promoted with vanadium oxide has been investigated. Three different vanadium promoted Pd/Al2O3 catalysts with the same composition but synthesized employing sequential and co-impregnation were tested for the total oxidation of propane. The order of impregnation was critical to produce high activity catalysts. Vanadium and palladium co-impregnation on the Al2O3 support led to the most active catalyst, whereas the step-wise impregnated catalysts show a catalytic performance similar to or slightly better than unpromoted palladium catalysts. The high activity of the co-impregnated catalysts is related to the particle size and oxida…
Redox Systems, Oxidative Stress, and Antioxidant Defences in Health and Disease
2021
Reactive oxygen and nitrogen species (RONS) play a key role in the regulation of cell survival. While adequate levels of RONS are essential to sustain cell proliferation and survival, disruption of the endocellular redox state induces cell dysfunction and death. Indeed, under physiological conditions, a balance between the generation and elimination of RONS ensures the proper function of redox-sensitive signalling proteins. Conversely, alterations to the redox homeostasis may disrupt the function of key transcription factors, signaltransduction pathways and cell-death regulators. Along these lines, understanding the mechanisms underlying cellular redox homeostasis may help to develop nutrac…
Redox regulation of enzymatic activity and proteolytic susceptibility of ribulose-1,5-bisphosphate carboxylase/oxygenase fromEuglena gracilis.
1992
The activity of ribulose-1,5-bisphosphate carboxylase/oxygenase fromEuglena gracilis decays steadily when exposed to agents that induce oxidative modification of cysteine residues (Cu(2+), benzofuroxan, disulfides, arsenite, oxidized ascorbate). Inactivation takes place with a concomitant loss of cysteine sulfhydryl groups and dimerization of large subunits of the enzyme. 40% activity loss induced by the vicinal thiol-reagent arsenite is caused by modification of a few neighbor residues while the almost complete inactivation achieved with disulfides is due to extensive oxidation leading to formation of mixed disulfides with critical cysteines of the protein. In most cases oxidative inactiva…
A pan-cancer analysis shows immunoevasive characteristics in NRF2 hyperactive squamous malignancies
2023
The NRF2 pathway is frequently activated in various cancer types, yet a comprehensive analysis of its effects across different malignancies is currently lacking. We developed a NRF2 activity metric and utilized it to conduct a pan-cancer analysis of oncogenic NRF2 signaling. We identified an immunoevasive phenotype where high NRF2 activity is associated with low interferon-gamma (IFNγ), HLA-I expression and T cell and macrophage infiltration in squamous malignancies of the lung, head and neck area, cervix and esophagus. Squamous NRF2 overactive tumors comprise a molecular phenotype with SOX2/TP63 amplification, TP53 mutation and CDKN2A loss. These immune cold NRF2 hyperactive diseases are a…
A Reappraisal of Redox Melting in the Earth’s Mantle as a Function of Tectonic Setting and Time
2010
Redox melting refers to any process by which melt is generated by the contact of a rock with a fluid or melt with a contrasting oxidation state. It was originally applied to melting owing to the oxidation of reduced CH4and H2-bearing fluids in contact with more oxidized blocks in the mantle, particularly recycled crustal blocks.This oxidation mechanism causes an increase in the activity of H2O by the reaction of CH4 with O2, and the increased aH2O causes a rapid drop in the solidus temperature, and is here termed hydrous redox melting (HRM). Recently, a second redox melting mechanism (carbonate redox melting; CRM) has been discovered that operates in more oxidized conditions, and may post-d…
Role of peroxiredoxin 6 in the chondroprotective effects of microvesicles from human adipose tissue-derived mesenchymal stem cells
2021
Este artículo se encuentra disponible en la página web de la revista en la siguiente URL: https://www.sciencedirect.com/science/article/pii/S2214031X21000656?via%3Dihub Background: Osteoarthritis (OA) is a joint disease characterized by cartilage degradation, low-grade synovitis and subchondral bone alterations. In the damaged joint, there is a progressive increase of oxidative stress leading to disruption of chondrocyte homeostasis. The modulation of oxidative stress could control the expression of inflammatory and catabolic mediators involved in OA. We have previously demonstrated that extracellular vesicles (EVs) present in the secretome of human mesenchymal stem cells from adipose tissu…
Structure, mechanism and regulation of peroxiredoxins.
2003
Peroxiredoxins (Prxs) are a ubiquitous family of antioxidant enzymes that also control cytokine-induced peroxide levels which mediate signal transduction in mammalian cells. Prxs can be regulated by changes to phosphorylation, redox and possibly oligomerization states. Prxs are divided into three classes: typical 2-Cys Prxs; atypical 2-Cys Prxs; and 1-Cys Prxs. All Prxs share the same basic catalytic mechanism, in which an active-site cysteine (the peroxidatic cysteine) is oxidized to a sulfenic acid by the peroxide substrate. The recycling of the sulfenic acid back to a thiol is what distinguishes the three enzyme classes. Using crystal structures, a detailed catalytic cycle has been deriv…