embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high densityof active sites and the elimination or reduction of Fenton-type processes. The latter are initiated byhydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.
Copper can efficiently electro‐catalyze carbon dioxide reduction to C2+ products (C2H4, C2H5OH, n‐propanol). However, the correlation between the activity and active sites remains ambiguous, impeding further improvements in their performance. The facet effect of copper crystals to promote CO adsorption and C−C coupling and consequently yield a superior selectivity for C2+ products is described. We achieve a high Faradaic efficiency (FE) of 87 % and a large partial current density of 217 mA cm−2 toward C2+ products on Cu(OH)2‐D at only −0.54 V versus the reversible hydrogen electrode in a flow‐cell electrolyzer. With further coupled to a Si solar cell, record‐high solar conversion efficiencies of 4.47 % and 6.4 % are achieved for C2H4 and C2+ products, respectively. This study provides an in‐depth understanding of the selective formation of C2+ products on Cu and paves the way for the practical application of electrocatalytic or solar‐driven CO2 reduction.
BackgroundLow back pain and sciatica caused by intervertebral disc (IVD) disease are associated with inflammatory responses. The cytokine interleukin 17 (IL-17) is elevated in herniated and degenerated IVD tissues and acts as a regulator of disc inflammation. The objective of this study was to investigate the involvement of IL-17A in IVD inflammatory response and to explore the mechanisms underlying this response.MethodsCells were isolated from nucleus pulposus (NP) tissues collected from patients undergoing surgeries for IVD degeneration. The concentrations of COX2 and PGE2, as well as of select proteins involved in the mitogen-activated protein kinase (MAPK)/activating protein-1 (AP-1) pathway, were quantified in NP cells after exposure to IL-17 with or without pretreatment with MAPK or AP-1 inhibitors.ResultsOur results showed that IL-17A increased COX2 expression and PGE2 production via the activation of MAPKs, including p38 kinase and Jun N-terminal kinase (JNK). Moreover, IL-17A-induced COX2 and PGE2 production was shown to rely on p38/c-Fos and JNK/c-Jun activation in an AP-1-dependent manner.ConclusionIn summary, our results indicate that IL-17A enhances COX2 expression and PGE2 production via the p38/c-Fos and JNK/c-Jun signalling pathways in NP cells to mediate IVD inflammation.
To advance the widespread implementation of electrochemical energy storage and conversion technologies, the development of inexpensive electrocatalysts is imperative. In this context, Fe/N/C-materials represent a promising alternative to the costly noble metals currently used to catalyze the oxygen reduction reaction (ORR), and also display encouraging activities for the reduction of CO 2 . Nevertheless, the application of these materials in commercial devices requires further improvements in their performance and stability that are currently hindered by a lack of understanding of the nature of their active sites and the associated catalytic mechanisms. With this motivation, herein the authors exploit the high sensitivity of modulation excitation X-ray absorption spectroscopy toward species undergoing potential-induced changes to elucidate the operando local geometry of the active sites in two sorts of Fe/N/C-catalysts. While the ligand environment of a part of both materials' sites appears to change from six-/five-to fourfold coordination upon potential decrease, they differ substantially when it comes to the geometry of the coordination sphere, with the more ORRactive material undergoing more pronounced restructuring. Furthermore, these time-resolved spectroscopic measurements yield unprecedented insights into the kinetics of Fe-based molecular sites' structural reorganization, identifying the oxidation of iron as a rate-limiting process for the less ORR-active catalyst.
The
electrochemical reduction of CO2 (eCO2RR) using
renewable energy is an effective approach to pursue carbon
neutrality. The eCO2RR to CO is indispensable in promoting
C–C coupling through bifunctional catalysis and achieving cascade
conversion from CO2 to C2+. This work investigates
a series of M/N–C (M = Mn, Fe, Co, Ni, Cu, and Zn) catalysts,
for which the metal precursor interacted with the nitrogen-doped carbon
support (N–C) at room temperature, resulting in the metal being
present as (sub)nanosized metal oxide clusters under ex situ conditions, except for Cu/N–C and Zn/N–C. A volcano
trend in their activity toward CO as a function of the group of the
transition metal is revealed, with Co/N–C exhibiting the highest
activity at −0.5 V versus RHE, while Ni/N–C
shows both appreciable activity and selectivity. Operando X-ray absorption spectroscopy shows that the majority of Cu atoms
in Cu/N–C form Cu0 clusters during eCO2RR, while Mn/, Fe/, Co/, and Ni/N–C catalysts maintain the
metal hydroxide structures, with a minor amount of M0 formed
in Fe/, Co/, and Ni/N–C. The superior activity of Fe/, Co/,
and Ni/N–C is ascribed to the phase contraction and the HCO3
– insertion into the layered structure of
metal hydroxides. Our work provides a facile synthetic approach toward
highly active and selective electrocatalysts to convert CO2 into CO. Coupled with state-of-the-art NiFe-based anodes in a full-cell
device, Ni/N–C exhibits >80% Faradaic efficiency toward
CO
at 100 mA cm–2.
This study was conducted in order to investigate the function of IL-21 in intervertebral disc degeneration. The serum concentration of IL-21 in patients with lumbar disc herniation (LDH) was examined by ELISA. Immunohistochemistry and western blot analysis were performed to detect the expression of IL-21, a disintegrin and metalloproteinase with thrombospondin motifs (ADAMTS-7), and tumor necrosis factor alpha (TNF-α) in degenerated intervertebral disc (IVD) tissues of human and rat. Moreover, nucleus pulposus (NP) cells were treated with 0, 10, 100, and 1000 ng/mL of IL-21 cytokine with and without AG490. TNF-α, ADAMTS-7, and matrix metalloproteinases-13 (MMP-13) mRNA expression was determined by RT-PCR. The expression of signal transducers and activators of transcription, STAT-1, STAT-3, and STAT-5b, was detected by western blot. IL-21 concentration level is higher in the degenerated group and positively correlates with the visual analog score (VAS). IL-21, ADAMTS-7, and TNF-α can be detected in the degenerative NP tissues in both human and rat degenerated NP tissues. The mRNA expression of ADAMTS-7, TNF-α, and MMP-13 was enhanced after stimulation with IL-21. Compared to control, STAT-1, STAT-3, and STAT-5b expression was also enhanced after IL-21 treatment, with STAT-3 being the most significantly enhanced; furthermore, expression was significantly reduced after treatment with AG490. The mRNA expression of TNF-α was markedly reduced after treatment with AG490 compared to treatment with IL-21 only. IL-21 is involved in the pathological development of IVD degeneration and IL-21 could aggravate IVD degeneration by stimulating TNF-α through the STAT signaling pathway.
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