Cellular senescence is characterized by irreversible growth arrest incurred through either replicative exhaustion or by pro-oncogenic cellular stressors (radioactivity, oxidative stress, oncogenic ...activation). The enrichment of senescent cells in tissues with age has been associated with tissue dyshomeostasis and age-related pathologies including cancers, neurodegenerative disorders (e.g. Alzheimer's, Parkinson's, etc.) and metabolic disorders (e.g. diabetes). We identified copper accumulation as being a universal feature of senescent cells mouse embryonic fibroblasts (MEF), human prostate epithelial cells and human diploid fibroblasts in vitro. Elevated copper in senescent MEFs was accompanied by elevated levels of high-affinity copper uptake protein 1 (Ctr1), diminished levels of copper-transporting ATPase 1 (Atp7a) (copper export) and enhanced antioxidant defence reflected by elevated levels of glutathione (GSH), superoxide dismutase 1 (SOD1) and glutaredoxin 1 (Grx1). The levels of intracellular copper were further increased in senescent MEFs cultured in copper supplemented medium and in senescent Mottled Brindled (Mobr) MEFs lacking functional Atp7a. Finally, we demonstrated that the restoration/preservation of autophagic-lysosomal degradation in senescent MEFs following rapamycin treatment correlated with attenuation of copper accumulation in these cells despite a further decrease in Atp7a levels. This study for the first time establishes a link between Atp7a and the autophagic-lysosomal pathway, and a requirement for both to effect efficient copper export. Such a connection between cellular autophagy and copper homeostasis is significant, as both have emerged as important facets of age-associated degenerative disease.
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•Copper accumulation is a feature of cellular senescence.•Elevated copper in senescent cells is associated with impaired autophagic-lysosomal function.•Restoration/preservation of lysosomal function attenuates copper accumulation.•Both Atp7a and autophagic-lysosomal function are required for copper export.
Copper-containing sludge is a common by-product of industrial activities, particularly electroplating and metal processing. This type of sludge contains high concentrations of heavy metals such as ...copper, which can pose a potential threat to the environment. Therefore, its treatment and disposal require special attention. Due to its efficient mass and heat transfer characteristics, the suspended state technology has shown significant potential for application in a number of key processes, including the drying, decomposition, and reduction of copper-containing sludge. This paper presents an in-depth analysis of the current status of the application of the suspended state technology in the treatment of copper-containing sludge. Based on this analysis, a device for the treatment of copper-containing sludge in the suspended state was designed, through which the characteristics of copper-containing sludge in the oxidative decomposition and reduction phases are investigated. The research objects were gas concentration, temperature, contact state, and particle size time. Orthogonal experiments were initially employed to investigate the relationship between the influencing factors and the conversion rate of copper oxides. This was followed by a single-factor influence study, which led to the determination of the optimal process parameters for the decomposition experiments of the Cu-containing sludge in an oxidizing atmosphere. The 100 μm Cu-containing sludge was reacted with 10% O2 gas at a flow rate of 1 m/s for 3 min under the condition of 900 °C. The process parameters were then determined as follows: The research objects were gas concentration, temperature, contact state, and particle size time. Orthogonal experiments were employed to investigate the relationship between the influencing factors and the copper conversion rate. This was followed by a single-factor influence study, which determined the optimal process parameters for the copper-containing sludge reduction experiments. The 200 μm copper-containing sludge was reacted for 5 min at a flow rate of 7% carbon monoxide at a flow rate of 1.5 m/s under the condition of 800 °C.
Cuprous sulfide constitutes the primary component of copper concentrate and matte. Due to copper's sulfur-affinity characteristics, achieving one-step separation and recovery of copper and sulfur has ...always posed a challenge in copper metallurgy. Deep eutectic solvents (DESs) have emerged as environmentally friendly electrolytes for the separation and recycling of metals and their compounds. This study demonstrates the feasibility of dissolving Cu
2
S, reducing it to copper (Cu), and oxidizing it to sulfur (S) through electrolysis in Reline DES. Optimised electrolysis conditions of 1.2 V, 80 C, and 6 hours result in the deposition of pure nano-sized copper particles, ranging from 100-200 nm, and the production of sulfur particles with an average size of around 5 μm. The crystalline structure of the anode product is identified as S
12
and S
6
. When Cu
2
S is introduced into Reline, it dissolves CuCl
2
−
without disrupting the structure of the choline ion (Ch
+
). Furthermore, a kinetic study reveals that higher temperatures promote the redox processes of CuCl
2
−
Cu and S
2−
to S, enhancing the overall reaction rates. Additionally, the diffusion coefficient (
D
) of CuCl
2
increases with rising temperatures.
In this study, Cu
2
S was dissolved in Reline DES, and then separated and recovered as copper and sulfur by one-step electrolysis.
The human pathogen Salmonella enterica serovar Typhimurium (S. Typhimurium) contains a complex disulfide bond (Dsb) catalytic machinery. This machinery encompasses multiple Dsb thiol-disulfide ...oxidoreductases that mediate oxidative protein folding and a less-characterized suppressor of copper sensitivity (scs) gene cluster, associated with increased tolerance to copper. To better understand the function of the Salmonella Scs system, here we characterized two of its key components, the membrane protein ScsB and the periplasmic protein ScsC. Our results revealed that these two proteins form a redox pair in which the electron transfer from the periplasmic domain of ScsB (n-ScsB) to ScsC is thermodynamically driven. We also demonstrate that the Scs reducing pathway remains separate from the Dsb oxidizing pathways and thereby avoids futile redox cycles. Additionally, we provide new insight into the molecular mechanism underlying Scs-mediated copper tolerance in Salmonella. We show that both ScsB and ScsC can bind toxic copper(I) with femtomolar affinities and transfer it to the periplasmic copper metallochaperone CueP. Our results indicate that the Salmonella Scs machinery has evolved a dual mode of action, capable of transferring reducing power to the oxidizing periplasm and protecting against copper stress by cooperating with the cue regulon, a major copper resistance mechanism in Salmonella. Overall, these findings expand our understanding of the functional diversity of Dsb-like systems, ranging from those mediating oxidative folding of proteins required for infection to those contributing to defense mechanisms against oxidative stress and copper toxicity, critical traits for niche adaptation and survival.
Under ambient conditions, toluene can be oxidized selectively to benzaldehyde, an essential compound in the chemical industry. Copper(I) complexes were applied in combination with Ru(bipy)3(PF6)2 and ...dioxygen as the oxidant. A peroxido copper complex is formed as the active species. The copper(II) complex obtained after oxidation can be photochemically reduced to the starting copper(I) species, and the process can be repeated. More information can be found in the Research Article by C. Noß, R. Göttlich, and S. Schindler (DOI: 10.1002/chem.202301142).
Large volume, intermediate-felsic magma reservoirs are the source of melt and mineralising fluids which generate porphyry copper deposits. Cooling and crystallisation of hydrous magmas drives the ...exsolution and expulsion of a magmatic volatile phase—a process which remains challenging to constrain in porphyry Cu systems where the record of magma volatile compositions is rarely preserved. Here, we use the halogen compositions of apatite inclusions shielded as inclusions within zircon to constrain volatile evolution in magma reservoirs which pre-date and are synchronous with porphyry Cu mineralisation at Quellaveco, Southern Peru. Geochemical and textural data confirm that the zircon-included apatites escaped re-equilibration with hydrothermal fluids, unlike apatites found in the groundmass of the same rocks. We, therefore, recommend that future studies attempting to reconcile magmatic volatile budgets using apatite in porphyry Cu systems should focus on apatite inclusions in zircon. By combining the apatite inclusion data with numerical modelling, we find evidence that the magma reservoir sourcing porphyry Cu mineralisation remained fluid-saturated for the entire period recorded by apatite crystallisation. By contrast, the pre-mineralisation batholith shows more variable, potentially fluid-undersaturated behaviour. Our modelling suggests that in order to attain the porphyry melt volatile compositions inferred from apatite, the magma reservoir must have exsolved a large proportion of its volatile budget, consistent with having been held at high crystallinity (40–60% crystals). This crystallisation interval coincides with peak chlorine and copper extraction from intermediate-felsic magmas, and would have permitted efficient fluid migration and accumulation at the roof of the system. We suggest that the storage of large-volume, long-lived, crystal-rich magma reservoirs in magmatic arcs may be a critical step in generating world-class porphyry copper deposits.
The potent redox activity of copper is required for sustaining life. Mismanagement of its cellular pools, however, can result in oxidative stress and damage connected to aging, neurodegenerative ...diseases, and metabolic disorders. Therefore, copper homeostasis is tightly regulated by cells and tissues. Whereas copper and other transition metal ions are commonly thought of as static cofactors buried within protein active sites, emerging data points to the presence of additional loosely bound, labile pools that can participate in dynamic signalling pathways. Against this backdrop, we review advances in sensing labile copper pools and understanding their functions using synthetic fluorescent indicators. Following brief introductions to cellular copper homeostasis and considerations in sensor design, we survey available fluorescent copper probes and evaluate their properties in the context of their utility as effective biological screening tools. We emphasize the need for combined chemical and biological evaluation of these reagents, as well as the value of complementing probe data with other techniques for characterizing the different pools of metal ions in biological systems. This holistic approach will maximize the exciting opportunities for these and related chemical technologies in the study and discovery of novel biology of metals.
This review surveys fluorescent probes for copper, emphasizing desirable criteria for their effective use for discovery and study of new metal biology.
Facing greenhouse effects and the rapid exhaustion of fossil fuel, COsub.2 electrochemical reduction presents a promising method of environmental protection and energy transformation. Low onset ...potential, large current density, high faradaic efficiency (FE), and long-time stability are required for industrial production, due to economic costs and energy consumption. This minireview showcases the recent progress in catalyst design and engineering technology in COsub.2 reduction reaction (COsub.2RR) on copper based-catalysts. We focus on strategies optimizing the performance of copper-based catalysts, such as single-atom catalysts, doping, surface modification, crystal facet engineering, etc., and reactor design including gas diffusion layer, membrane electrode assembly, etc., in enhancing target electroreduction products including methane, methanol, ethylene, and Csub.2+ oxygenates. The determination of the correlation and the developed technology might be helpful for future applications in the industry.
Recently, plasmonic copper sulfide (Cu2–x S) nanocrystals (NCs) have attracted much attention as materials for photothermal therapy (PTT). Previous reports have correlated photoinduced cell death to ...the photothermal heat mechanism of these NCs, and no evidence of their photodynamic properties has been reported yet. Herein we have prepared physiologically stable near-infrared (NIR) plasmonic copper sulfide NCs and analyzed their photothermal and photodynamic properties, including therapeutic potential in cultured melanoma cells and a murine melanoma model. Interestingly, we observe that, besides a high PTT efficacy, these copper sulfide NCs additionally possess intrinsic NIR induced photodynamic activity, whereupon they generate high levels of reactive oxygen species. Furthermore, in vitro and in vivo acute toxic responses of copper sulfide NCs were also elicited. This study highlights a mechanism of NIR light induced cancer therapy, which could pave the way toward more effective nanotherapeutics.
Copper (Cu), an essential micronutrient, plays an essential role in several physiological processes, including cell proliferation and angiogenesis; however, its dysregulation induces oxidative stress ...and inflammatory responses. Significant Cu accumulation is observed in several tumor tissues. The bioavailability of intracellular Cu is tightly controlled by Cu transporters, including Cu transporter 1 (CTR1) and Cu-transporting P-type ATPase α and β (ATP7A and ATP7B), and Cu chaperones, including Cu chaperone for superoxide dismutase 1 (CCS) and antioxidant-1 (Atox-1). In several tumor tissues, these abnormalities that induce intracellular Cu accumulation are involved in tumor progression. In addition, functional disturbance in Cu-containing secretory enzymes, such as superoxide dismutase 3 (SOD3), and lysyl oxidase enzymes (LOX and LOXL1–4) with abnormal Cu dynamics plays a key role in tumor metastasis. For example, the loss of SOD3 in tumor tissues induces oxidative stress, which promotes neovascularization and epithelial-to-mesenchymal transition (EMT). LOX promotes collagen crosslinking, which functions in the metastatic niche formation. Accordingly, restricted Cu regulation may be a novel strategy for the inhibition of tumor metastasis. However, it is unclear how these Cu disturbances occur in tumor tissues and the exact molecular mechanisms underlying Cu secretory enzymes. In this review article, I discuss the role of Cu transporters, Cu chaperones, and Cu-containing secretory enzymes in tumor progression to better understand the role of Cu homeostasis in tumor tissues.
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