Unraveling the pH-Dependent Oxygen Reduction Performance on Single-Atom Catalysts: From Single- to Dual-Sabatier Optima.

Metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) have emerged as a potential substitute for the costly platinum-group catalysts in oxygen reduction reaction (ORR). However, several critical aspects of M-N-C SACs in ORR remain poorly understood, including their pH-dependent activity, selectivity for 2- or 4-electron transfer pathways, and the identification of the rate-determining steps. Herein, by analyzing >100 M-N-C structures and >2000 sets of energetics, we unveil a pH-dependent evolution in ORR activity volcanos─from a single peak in alkaline media to a double peak in acids. We found that this pH-dependent behavior in M-N-C catalysts fundamentally stems from their moderate dipole moments and polarizability for O* and HOO* adsorbates, as well as unique scaling relations among ORR adsorbates. To validate our theoretical discovery, we synthesized a series of molecular M-N-C catalysts, each characterized by well-defined atomic coordination environments. Impressively, the experiments matched our theoretical predictions on kinetic current, Tafel slope, and turnover frequency in both acidic and alkaline environments. These new insights also refine the famous Sabatier principle by emphasizing the need to avoid an "acid trap" while designing M-N-C catalysts for ORR or any other pH-dependent electrochemical applications.

Single-cell RNA analysis of chemokine expression in heterogeneous CD14+ monocytes with lipopolysaccharide-induced bone resorption.

Lipopolysaccharide (LPS)-induced bone resorption has normally been found in inflammatory bone diseases, but the underlying mechanism is currently unclear. Since LPS binds to CD14 and activates Toll-like receptor 4 (TLR4) in monocytes, the present study focused on CD14+ monocytes and observed their responses after LPS treatment during the progression of local bone destruction. CD14+ monocytes were obtained from human peripheral blood mononuclear cells (PBMCs) by magnetic cell separation (MACS), and their classification was confirmed by fluorescence-activated cell sorting (FACS). Single-cell RNA sequencing (scRNA-seq) was further utilized to analyze their subpopulations, and the results showed that physiological CD14+ monocytes were heterogeneous and divided into 6 subsets, that could be easily agitated. After priming with a suitable concentration of LPS, heterogeneous CD14+ monocytes became pathological and expressed a large number of chemokines as a "cascade effect". Some of these chemokines have been validated in an animal model of mouse calvarial bone invasion. Taken together, our research has linked enhanced chemokine expression with stimulation of heterogeneous CD14+ monocytes, and indicated that inflammatory responses caused by microbiome infection are responsible for the recruitment and mobilization of CD14+ monocytes into bone resorption sites, which may explain the pathogenesis of LPS-associated bone diseases.

Cyclic Stretch Force Induces Periodontal Ligament Cells to Secrete Exosomes That Suppress IL-1ß Production Through the Inhibition of the NF-κB Signaling Pathway in Macrophages.

In the oral mechanical environment, periodontal ligament cells (PDL cells) contribute to maintaining periodontal tissue homeostasis. Recent studies showed that exosomes, which are small vesicles secreted by various types of cells, play a pivotal role in cell-to-cell communication in biological processes. We examined the secretion of exosomes from PDL cells stimulated with cyclic stretch and their role in the inflammatory response of macrophages using the human macrophage cell line THP-1 and human primary monocytes/macrophages. We prepared supernatants from human PDL cells (PDL-sup) stimulated with cyclic stretch. The treatment of macrophages with PDL-sup, but not PDL-sup from unstimulated PDL cells, inhibited the production of IL-1ß in LPS/nigericin-stimulated macrophages. The pretreatment of PDL cells with GW4869, an inhibitor of exosome secretion, or siRNA for Rab27B, which controls exosome secretion, abrogated the inhibitory effects of PDL-sup. A transmission electron microscopy analysis demonstrated the existence of exosomes with diameters ranging between 30 and 100 nm in PDL-sup, suggesting that exosomes in PDL-sup contribute to this inhibition. An immunofluorescence microscopy analysis revealed that exosomes labeled with PKH67, a fluorescent dye, were incorporated by macrophages as early as 2 h after the addition of exosomes. Purified exosomes inhibited IL-1ß production in LPS/nigericin-stimulated macrophages and the nuclear translocation of NF-κB as well as NF-κB p65 DNA-binding activity in LPS-stimulated macrophages, suggesting that exosomes suppress IL-1ß production by inhibiting the NF-κB signaling pathway. Our results indicate that PDL cells in mechanical environments contribute to the maintenance of periodontal immune/inflammatory homeostasis by releasing exosomes.

Current concepts in odontohypophosphatasia form of hypophosphatasia and report of two cases.

BACKGROUND: Hypophosphatasia is a rare inherited disease derived from mutations in tissue non-specific alkaline phosphatase genes, with typical oral symptoms including short root anomaly and dysplasia of dentin or cementum. CASE PRESENTATION: Two young female patients presented with short root anomaly with a history of premature loss of deciduous and/or permanent teeth. The laboratory and imaging investigations were performed. One case was diagnosed as odontohypophosphatasia concurrent with hyperthyroidism, the other was odontohypophosphatasia concurrent with multiple radicular cysts. CONCLUSION: This report presents two cases of odontohypophosphatasia, a rare disease which is difficult to be diagnosed, and highlights that the history of premature loss of deciduous and/or permanent teeth, oral manifestation and laboratory tests are crucial for clinical diagnosis.

Cyclic Fatigue Resistance and Force Generated by OneShape Instruments during Curved Canal Preparation.

OBJECTIVES: To evaluate the cyclic fatigue resistance and the force generated by OneShape files during preparation of simulated curved canals. METHODS: Six OneShape files (the test) and six ProTaper F2 files (the control) were subject to the bending ability test. Another thirty files of each type were used to prepare artificial canals (n = 60), which were divided into 3 groups according to respective curvatures of the canals (30°, 60°, and 90°). The numbers of cycles to fatigue (NCF) as well as the positive and negative forces that were generated by files during canal preparation were recorded. The scanning electron microscopy was applied to detect the fracture surfaces. RESULTS: Compared with ProTaper F2 files, the bending loads of OneShape files were significantly lower at deflections of 45°(P < .05), 60° (P < .05) and 75° (P < .01). No significant difference was found at 30°. OneShape files presented a higher NCF in both 60° and 90° canals than the control (P < .01). No significant difference of NCF was found between OneShape and ProTaper files in 30° canals. During the preparation of 30° canals by both files, the negative forces were dominant. With the increase of the curvature, more positive forces were observed. When the OneShape Files were compared with the control, significant different forces were found at D3 and D2 (P < .05) in 30° canals, at D2 (P < .05), D1 (P < .01) and D0 (P < .01) in 60° canals, and at D4 and D3 (P < .01) in 90° canals. CONCLUSIONS: OneShape files possessed a reliable flexibility and cyclic fatigue resistance. According to the assessments of the forces generated by files, OneShape instruments performed in a more fatigue-resistant way during curved canal preparation, compared with the ProTaper F2 files.