Defects have been found to enhance the electrocatalytic performance of NiFe‐LDH for oxygen evolution reaction (OER). Nevertheless, their specific configuration and the role played in regulating the ...surface reconstruction of electrocatalysts remain ambiguous. Herein, cationic vacancy defects are generated via aprotic‐solvent‐solvation‐induced leaking of metal cations from NiFe‐LDH nanosheets. DFT calculation and in situ Raman spectroscopic observation both reveal that the as‐generated cationic vacancy defects tend to exist as VM (M=Ni/Fe); under increasing applied voltage, they tend to assume the configuration VMOH, and eventually transform into VMOH‐H which is the most active yet most difficult to form thermodynamically. Meanwhile, with increasing voltage the surface crystalline Ni(OH)x in the NiFe‐LDH is gradually converted into disordered status; under sufficiently high voltage when oxygen bubbles start to evolve, local NiOOH species become appearing, which is the residual product from the formation of vacancy VMOH‐H. Thus, we demonstrate that the cationic defects evolve along with increasing applied voltage (VM → VMOH → VMOH‐H), and reveal the essential motif for the surface restructuration process of NiFe‐LDH (crystalline Ni(OH)x → disordered Ni(OH)x → NiOOH). Our work provides insight into defect‐induced surface restructuration behaviors of NiFe‐LDH as a typical precatalyst for efficient OER electrocatalysis.
Along with increasing voltage during the OER process, the structural evolution of cationic defects within NiFe‐LDH, where the simple vacancy VM changes to VMOH and then to the most reactive VMOH‐H, and the surface restructuration, where surface crystalline Ni(OH)x is converted to disordered Ni(OH)x and then to the surface local NiOOH species, are voltage‐regulated concurrent events defining the eventual catalytic performance of the precatalyst.
Calixarene-capped Co32 clusters are constructed by a sodalite CoII 24 cage and an encapsulated CoIII 8 cube. The spherical units are arranged into three isomeric structures, two of which are stacked ...by the bcc lattices and the third of which is assembled by the cubic closest packing of the spherical units.
IBD (inflammatory bowel disease) is a chronic inflammatory disease of the gastrointestinal tract with increasing incidence worldwide. Multiple factors, such as genetic background, environmental and ...luminal factors, and mucosal immune dysregulation, have been implicated in the cause of IBD, although the cause of the disease remains unknown. IL-12 and IL-23 and their downstream signaling pathways participate in the pathogenesis of inflammatory bowel disease. Early and aggressive treatment with biologic therapies or novel small molecules is needed to decrease complications and the need for hospitalization and surgery. The landscape of inflammatory bowel disease (IBD) treatment has tremendously improved with the development of biologics and small molecule drugs. Several novel biologics and small molecule drugs targeting IL-12 and IL-23 and their downstream targets have shown positive efficacy and safety data in clinical trials, and several drugs have been approved for the treatment of IBD. In the future, numerous potential emerging therapeutic options for IBD treatment are believed to come to the fore, achieving disease cure.
This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear TbIII (1 and 3) and DyIII (2 and 4) complexes supported by p-phenylthiacalix4arene ...(H4PTC4A) and p-tert-butylthiacalix4arene (H4TC4A). All four frameworks can be formulated as LnIII 4(PTC4A/TC4A)2(μ4-OH)Cl3(CH3OH)2(H2O)3, and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (μ4-OH)Ln4 cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-LnIII energy transfer for compounds 1−3 and H4PTC4A is a more efficient “antenna” than H4TC4A. The DyIII compounds exhibit slow magnetic relaxation behavior of single-molecule magnet nature. The substitution of the t-Bu group with a phenyl group at the up-rim of thiacalix4arene leads to different extended structures and physical properties of as-synthesized compounds.
The precise mechanism through which macroautophagy/autophagy affects psoriasis is poorly understood. Here, we found that keratinocyte (KC) autophagy, which was positively correlated with psoriatic ...severity in patients and mouse models and could be inhibited by mitogen-activated protein kinase (MAPK) family inactivation. The impairment of autophagic flux alleviated psoriasisform inflammation. We also found that an autophagy-based unconventional secretory pathway (autosecretion) dependent on ATG5 (autophagy related 5) and GORASP2 (golgi reassembly stacking protein 2) promoted psoriasiform KC inflammation. Moreover, the alarmin HMGB1 (high mobility group box 1) was more effective than other autosecretory proteins in regulating psoriasiform cutaneous inflammation. HMGB1 neutralization in autophagy-efficient KCs eliminated the differences in psoriasiform inflammation between Krt14
+/+
-Atg5
f/f
KCs and Krt14
Cre/+
-atg5
f/f
KCs, and conversely, recombinant HMGB1 almost completely restored psoriasiform inflammation in Krt14
Cre/+
-atg5
f/f
KCs in vivo. These results suggest that HMGB1-associated autosecretion plays a pivotal role in cutaneous inflammation. Finally, we demonstrated that Krt14
Cre/+
-hmgb1
f/f
mice displayed attenuated psoriatic inflammation due to the essential crosstalk between KC-specific HMGB1-associated autosecretion and γδT cells. Thus, this study uncovered a novel autophagy mechanism in psoriasis pathogenesis, and the findings imply the clinical significance of investigating and treating psoriasis.
Abbreviations: 3-MA: 3-methyladenine; ACTB: actin beta; AGER: advanced glycosylation end-product specific receptor; Anti-HMGB1: anti-HMGB1 neutralizing antibody; Anti-IL18: anti-IL18 neutralizing antibody; Anti-IL1B: anti-IL1B neutralizing antibody; ATG5: autophagy related 5; BAF: bafilomycin A
1
; BECN1: beclin 1; CASP1: caspase 1; CCL: C-C motif chemokine ligand; CsA: cyclosporine A; ctrl shRNA: lentivirus harboring shRNA against control; CXCL: C-X-C motif chemokine ligand; DCs: dendritic cells; DMEM: dulbecco's modified Eagle's medium; ELISA: enzyme-linked immunosorbent assay; EM: electron microscopy; FBS: fetal bovine serum; GORASP2 shRNA: lentivirus harboring shRNA against GORASP2; GORASP2/GRASP55: golgi reassembly stacking protein 2; GR1: a composite epitope between LY6 (lymphocyte antigen 6 complex) locus C1 and LY6 locus G6D antigens; H&E: hematoxylin and eosin; HMGB1: high mobility group box 1; HMGB1 shRNA: lentivirus harboring shRNA against HMGB1; IFNG/IFN-γ: interferon gamma; IL17A: interleukin 17A; IL18: interleukin 18; IL1A/IL-1α: interleukin 1 alpha; IL1B/IL-1β: interleukin 1 beta; IL22/IL-22: interleukin 22; IL23A: interleukin 23 subunit alpha; IL23R: interleukin 23 receptor; IMQ: imiquimod; ITGAM/CD11B: integrin subunit alpha M; ITGAX/CD11C: integrin subunit alpha X; IVL: involucrin; KC: keratinocyte; KD: knockdown; KO: knockout; Krt14
+/+
-Atg5
f/f
mice: mice bearing an Atg5 flox allele, in which exon 3 of the Atg5 gene is flanked by two loxP sites; Krt14
+/+
-Hmgb1
f/f
: mice bearing an Hmgb1 flox allele, in which exon 2 to 4 of the Hmgb1 gene is flanked by two loxP sites; Krt14
Cre/+
-atg5
f/f
mice: keratinocyte-specific atg5 knockout mice generated by mating Atg5-floxed mice with mice expressing Cre recombinase under the control of the promoter of Krt4; Krt14
Cre/+
-hmgb1
f/f
mice: keratinocyte-specific hmgb1 knockout mice generated by mating Hmgb1-floxed mice with mice expressing Cre recombinase under the control of the promoter of Krt14; Krt14-Vegfa mice: mice expressing 164-amino acid Vegfa splice variant recombinase under the control of promoter of Krt14; LAMP1: lysosomal associated membrane protein 1; LDH: lactate dehydrogenase; LORICRIN: loricrin cornified envelope precursor protein; M5: TNF, IL1A, IL17A, IL22 and OSM in combination; MAP1LC3/LC3: microtubule associated protein 1 light chain 3; MAPK: mitogen-activated protein kinase; MKI67: marker of proliferation Ki-67; MTT: thiazolyl blue tetrazolium bromide; NFKB/NF-κB: nuclear factor kappa B; NHEKs: primary normal human epidermal keratinocytes; NS: not significant; OSM: oncostatin M; PASI: psoriasis area and severity index; PtdIns3K: class III phosphatidylinositol 3-kinase; qRT-PCR: quantitative RT-PCR; RELA/p65: RELA proto-oncogene, NF-kB subunit; rHMGB1: recombinant HMGB1; rIL18: recombinant interleukin 18; rIL1B: recombinant interleukin 1 beta; S100A: S100 calcium binding protein A; SQSTM1/p62: sequestosome 1; T17: IL17A-producing T; TCR: T-cell receptor; tcrd KO mice: tcrd (T cell receptor delta chain) knockout mice, which show deficient receptor expression in all adult lymphoid and epithelial organs; TLR: toll-like receptor; TNF/TNF-α: tumor necrosis factor; WOR: wortmannin; WT: wild-type; γδT17 cells: IL17A-producing γδ T cells.
•A hierarchical porous carbonaceous framework with abundant single-atom WNx active sites and numerous ultrafine WN nanoclusters was prepared.•The optimal W/N/C exhibits outstanding trifunctional ...catalytic activity and robust durability towards IOR/ORR/IDR.•Homemade rechargeable zinc-air/iodide batteries using the multifunctional W/N/C catalyst as cathode catalysts demonstrates a high peak energy density of 141.9 mW cm−2.
Different from the conventional Zinc-Air batteries which only involves oxygen reduction and evolution (ORR/OER) in the cathode, the cathode of rechargeable zinc–air/iodide hybrid batteries (ZAIHBs), with the addition of I− species, involves I− electrooxidation (IOR) during charging and oxygen/iodate reduction (ORR and IDR) during discharging. This work reports the synthesis of a hierarchically porous tungsten-based nitrogen-doped carbon framework (W/N/C) with abundant WNx active sites and numerous ultrafine WN nanoclusters and explores their application as a trifunctional IOR/ORR/IDR electrocatalyst for ZAIHBs. The formation mechanism of ZIF-8-derived W/N/C framework as well as its structural and compositional features were investigated. The catalyst demonstrates high trifunctional catalytic activity and robust durability towards IOR/ORR/IDR in alkaline condition, owing to the uniform copresence of the numerous sub-nanometer-sized WN nanoclusters and the abundant single atom WNx sites in the hierarchically structured carbon framework. When applied in homemade ZAIHBs, it revealed a high peak energy density (141.9 mW cm−2) and remarkable cycling stability (65 h), outperforming the commercial Pt/C catalysts. This work demonstrates the multi-functional electrocatalytic activity of tungsten-based non-noble metal electrocatalyst for high-performance ZAIHBs.
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Recently, the stability of DC microgrids has attracted increasing attention. The traditional stability analysis method cannot not meet the requirements for the complexity and bidirectional energy ...flow of the system. In this paper, a passivity-based stability criterion (PBSC) is proposed to analyze the stability of the cascade system. In order to realize the passivity of the system, an improved feedback control method based on the traditional double-loop control strategy is proposed, which will improve the stability region and guarantee the passivity of the system. Moreover, a Buck-CPL simulation model is established based on MATLAB/Simulink R2008, and the correctness of the theoretical analysis is verified by experiments.
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•N-doped carbon-coated TiN (TiN/C) was fabricated using pyrrole as carbon source.•The TiN/C supercapacitor retains 92% of the initial capacitance after 5000 cycles.•The carbon coating ...raises the anti-oxidation yet remains the activity of TiN.•Asymmetric TiN/C//MnO2 supercapacitor reveals high energy and power density.
TiN used as supercapacitor (SC) electrode in aqueous electrolyte is prone to suffering from oxidation, leading to poor electrical conductivity and electrochemical activity. In this work, TiN nanoparticles were synthesized at 530°C by the reaction between Ti powder and NH4Cl in stainless steel autoclaves, which further reacted with pyrrole at 550°C to yield N-doped carbon-coated TiN (TiN/C) with mesopores. TiN/C as electrode material for SC exhibits excellent electrochemical performance in 1M KOH electrolyte, achieving a specific capacitance of 102.6Fg−1 at a current density of 1Ag−1 and retaining a specific capacitance of 94.4Fg−1 after 5000 cycles (corresponding to capacitance retention of 92%). In particular, the TiN/C with a low operation voltage window and superior long-term cycling stability is a promising negative electrode for asymmetric SCs. The SC constructed by TiN/C and MnO2 reveals a high energy density of 17.2Whkg−1 as well as excellent cycling stability in 1M KOH electrolyte. The protective amorphous carbon coated on the TiN nanoparticles significantly improves the anti-oxidizability of TiN yet preserves the electrochemical activity via the loose carbon structure. Therefore, the TiN/C nanocomposite with low cost is promising and applicable in SCs.
IL-37 is a potent inhibitor of innate immunity by shifting the cytokine equilibrium away from excessive inflammation. Psoriasis is thought to be initiated by abnormal interactions between the ...cutaneous keratinocytes and systemic immune cells, triggering keratinocyte hyperproliferation. In the current study, we assessed IL-37 in two well-known psoriasis models: a human keratinocyte cell line (HaCaT) and the keratin 14 VEGF-A-transgenic mouse model. First, we used the HaCaT cell line, which was transiently transfected with an overexpressing IL-37 vector, and tested the effect of IL-37 on these cells using a mixture of five proinflammatory cytokines. IL-37 was effective in suppressing the production of CXCL8, IL-6, and S100A7, which were highly upregulated by the mixture of five proinflammatory cytokines. Keratin 14 VEGF-A-transgenic mice were treated with plasmid coding human IL-37 sequence-formulated cationic liposomes, and we observed potent immunosuppressive effects over the 18-d period. In this model, we observed reduced systemic IL-10 levels, local IFN-γ gene transcripts, as well as mild mast cell infiltration into the psoriatic lesions of the mice. Immunohistochemical analysis indicated that IL-37 was expressed by effector memory T cells, as well as macrophages, in human psoriatic plaques. In conclusion, our studies strongly indicate that IL-37 plays a potent immunosuppressive role in the pathogenesis of both experimental psoriasis models in vitro and in vivo by downregulating proinflammatory cytokines. Importantly, our findings highlight new therapeutic strategies that can be designed to use this immunosuppressive anti-inflammatory cytokine in psoriasis and other inflammatory cutaneous diseases.
Seawater electrocatalysis driven by renewable energy resources has long been considered as a promising approach for producing clean hydrogen. However, anodic electrode materials suffer from severe ...issues such as large overpotential and electrochemical corrosion during seawater electrolysis due to the existence of abundant chloride ions. Herein, we report a cationic defect engineering approach to tailoring the structure of NiFe layered double hydroxide (NiFe LDH) for the oxygen evolution reaction (OER) in an alkaline seawater-like solution. Impressively, the obtained cation defect-enriched NiFe LDH array exhibits an extremely low overpotential of 232 mV at 100 mA cm
−2
and excellent durability after 40 h electrolysis. The density functional theory (DFT) calculations show that CD-NiFe LDH-E facilitates charge transfer between metals (Ni/Fe) and oxygen (O), leading to inhibition of the competitive chlorine evolution reaction (CER). Moreover, homemade rechargeable Zn-air batteries with CD-NiFe LDH-E as the cathode are assembled, exhibiting high open circuit voltage (1.4 V) and excellent stability after 250 hours at a charging-discharging rate of 10 mA cm
−2
. The strategy is expected to pave the way for the future development of high-performance electrocatalysts toward seawater splitting.
A porous NiFe LDH with abundant cationic defects was synthesized to optimize interactions between active Ni species and adsorbates, exhibiting a highly efficient seawater electrolysis performance.
![Thiacalix[4]arene-Supported...](http://api.summon.serialssolutions.com/2.0.0/image/issn/XR4PS5YY4K/0020-1669/small "Thiacalix[4]arene-Supported Planar Ln4 (Ln = TbIII, DyIII) Clusters: Toward Luminescent and Magnetic Bifunctional Materials")
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