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Controlling the precise growth of atoms is necessary to achieve manipulation of atomic composition and atomic position, regulation of electronic structure, and an understanding of reactions at the atomic level. Herein, we report a facile method for ordered anchoring of zero-valent platinum and manganese atoms with single-atom thickness on graphdiyne under mild conditions. Due to strong and incomplete charge transfer between graphdiyne and metal atoms, the formation of metal clusters and nanoparticles can be inhibited. The size, composition and structure of the bimetallic nanoplates are precisely controlled by the natural structure-limiting effect of graphdiyne. Experimental characterization clearly demonstrates such a fine control process. Electrochemical measurements show that the active site of platinum-manganese interface on graphdiyne guarantees the high catalytic activity and selectivity (~100%) for alkene-to-diol conversion. This work lays a solid foundation for obtaining high-performance nanomaterials by the atomic engineering of active site.

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A challenge facing the chlor-alkali process is the lack of electrocatalyst with high activity and selectivity for the efficient industrial production of chlorine. Herein the authors report a new electrocatalyst that can generate multi-interface structure by in situ growth of graphdiyne on the surface of cobalt oxides (GDY/Co3O4), which shows great potential in highly selective and efficient chlorine production. This result is due to the strong electron transfer and high density charge transport between GDY and Co3O4 and the interconversion of the mixed valence states of the Co atoms itself. These intrinsic characteristics efficiently enhance the conductivity of the catalyst, facilitate the reaction kinetics, and improve the overall catalytic selectivity and activity. Besides, the protective effect of the formed GDY layer is remarkable endowing the catalyst with excellent stability. The catalyst can selectively produce chlorine in low-concentration of NaCl aqueous solution at room temperature and pressure with the highest Faraday efficiency of 80.67% and an active chlorine yield rate of 184.40 mg h-1 cm-2, as well as superior long-term stability.

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Advanced atomic-level heterointerface engineering provides a promising method for the preparation of next-generation catalysts. Traditional carbon-based heterointerface catalytic performance rely heavily on the undetermined defects in complex and demanding preparation processes, rendering it impossible to control the catalytic performance. Here, we present a general method for the controlled growth of metal atom arrays on graphdiyne (GDY/IrCuOx), and we are surprised to find strong heterointerface strains during the growth. We successfully controlled the thickness of GDY to regulate the heterointerface metal atoms and achieved compressive strain at the interface. Experimental and density functional theory calculation results show that the unique incomplete charge transfer between GDY and metal atoms leads to the formation of strong interactions and significant heterointerface compressive strain between GDY and IrCuOx, which results in high oxidation performances with 1000 mA cm-2 at a low overpotential of 283 mV and long-term stability at large current densities in alkaline simulated seawater. We anticipate that this finding will contribute to construction of high-performance heterogeneous interface structures, leading to the development of new generation of GDY-based heterojunction catalysts in the field of catalysis for future promising performance.

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Seeking organic cathode materials with low cost and long cycle life that can be employed for large-scale energy storage remains a significant challenge. This work has synthesized an organic compound, triphenazino[2,3-b](1,4,5,8,9,12-hexaazatriphenylene) (TPHATP), with as high as 87.16% yield. This compound has a highly π-conjugated and rigid molecular structure, which is synthesized by capping hexaketocyclohexane with three molecules of 2,3-diaminophenazine derived from low-cost o-phenylenediamine, and is used as a cathode material for assembling aqueous rechargeable zinc ion batteries. Both experiments and DFT calculations demonstrate that the redox mechanism of TPHATP is predominantly governed by H+ storage. The Zn-intercalation product of nitride-type compound, is too unstable to form in water. Moreover, the TPHATP cathode exhibits a capacity of as high as 318.3 mAh g-1 at 0.1 A g-1 , and maintained a stable capacity of 111.9 mAh g-1 at a large current density of 10 A g-1 for 5000 cycles with only a decay of 0.000512% per cycle. This study provides new insights into understanding pyrazine as an active redox group and offers a potential affordable aqueous battery system for grid-scale energy storage.

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Dental pulp stem cells (DPSCs) are a type of mesenchymal stem cells that can differentiate into odontoblast-like cells and protect the pulp. The differentiation of DPSCs can be influenced by biomaterials or growth factors that activate different signaling pathways in vitro or in vivo. In this review, we summarized six major pathways involved in the odontogenic differentiation of DPSCs, Wnt signaling pathways, Smad signaling pathways, MAPK signaling pathways, NF-kB signaling pathways, PI3K/AKT/mTOR signaling pathways, and Notch signaling pathways. Various factors can influence the odontogenic differentiation of DPSCs through one or more signaling pathways. By understanding the interactions between these signaling pathways, we can expand our knowledge of the mechanisms underlying the regeneration of the pulp-dentin complex.

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This study aimed to investigate the effectiveness of erbium-doped yttrium garnet (Er:YAG) laser and GLUMA desensitizer for dentin hypersensitivity in teeth affected by Molar-Incisor Hypomineralization (MIH). One hundred twenty children were randomly allocated to four groups: the control (Co) group, the desensitizer (De) group, the laser (La) group, and the laser + desensitizer (La + De) group. Outcome measures included Visual Analogue Scale (VAS) and 14-item Oral Health Impact Profile (OHIP-14) evaluation. For mean VAS scores, a significant reduction was found over time in all groups. Co and De groups, Co and La groups, Co and La + De groups, De and La + De groups, and La and La + De groups differed significantly (p < 0.05). For mean scores in all dimensions of OHIP-14 after treatment 6 months, the La + De group was significantly lower (p < 0.001). The La + De groups and the La groups as well as the La + De groups and the De groups differed significantly in total OHIP, functional limitation, physical disability, and psychological disability (p < 0.05). Physical pain between the La + De groups and the La groups and handicap between the La + De groups and De groups differed significantly (p < 0.05). The mean values of each dimension differed significantly between the group Co and the La + De group (p < 0.0001). Combination therapy of Er:YAG laser and GLUMA desensitizer had greater desensitizing effects and oral health-related quality improvement of life, which might be an effective alternative treatment in dentin hypersensitivity in MIH children.

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Oxidation and removal of highly toxic sulfides and amines are particularly important for environmental and human security but remain challenging. Here, incorporating an excellent photosensitizer, donor-acceptor-donor (D-A-D)-type 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic (H2L), into metal-organic frameworks (MOFs) has been manifested to promote the charge separation, affording four three-dimensional (3D) MOFs (isostructural 1-Co/1-Zn with Co2/Zn2 units, and 2-Gd/2-Tb with Gd/Tb-cluster chains) as photocatalysts in the visible light-driven air-O2-mediated catalytic oxidation and removal of hazardous phenylsulfides and benzylamines. Impressively, structure-property correlation illustrated that the transition metal centers assembled in MOFs play an important role in the photocatalytic activity, and we can conclude that 1-Zn can be a robust heterogeneous catalyst possessing good light adsorption and fast charge separation in oxidation removal reactions of both benzylamines and phenylsulfides under visible light irradiation and room temperature with excellent activity/selectivity, stability, and reusability.

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Graphdiyne, a sp/sp2 -cohybridized two-dimensional all- carbon material, has many unique and fascinating properties of alkyne-rich structures, large π conjugated system, uniform pores, specific unevenly-distributed surface charge, and incomplete charge transfer properties provide promising potential in practical applications including catalysis, energy conversion and storage, intelligent devices, life science, photoelectric, etc. These superior advantages have made graphdiyne one of the hottest research frontiers of chemistry and materials science and produced a series of original and innovative research results in the fundamental and applied research of carbon materials. In recent years, considerable advances have been made toward the development of graphdiyne-based multiscale catalysts for nitrogen fixation and ammonia synthesis at room temperatures and ambient pressures. This review aims to provide a comprehensive update in regard to the synthesis of graphdiyne-based multiscale catalysts and their applications in the synthesis of ammonia. The unique features of graphdiyne are highlighted throughout the review. Finally, it concludes with the discussion of challenges and future perspectives relating to graphdiyne.

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Organic dyes as non-noble metal photosensitizers have attracted increasing attention due to their environmental friendliness and sustainability but suffer from fast deactivation and low stability. Here, we reported a fruitful strategy by the confinement and stabilization of visible light-active signal unit organic dyes within the metal-organic frameworks (MOFs) and developed a series of heterogeneous photocatalysts dye@UiO-66s [dye = fluorescein (FL)/rhodamine B (RhB)/eosin Y (EY), UiO-66s = UiO-66, and Bim-UiO-66]. It has been demonstrated that the encapsulated dyes can effectively sensitize MOF hosts and dominate the band structures and photocatalytic activities of dye@UiO-66s regardless of the ligand functionalization of MOFs. Photocatalytic experiments showed that these dye@UiO-66s exhibit enhanced activities relative to free dyes and among them, FL@Bim-UiO-66 displays excellent efficiencies toward the green synthesis of new carbon-bridged annulations, [1,2,5]thiadiazole[3,4-g]benzoimidazoles in the yield of up to 98% at room temperature with outstanding stability and reusability. Furthermore, the intramolecular cyclization intermediate was captured and characterized by the single-crystal X-ray diffraction analysis.

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Ionizing radiation (IR) is associated with the occurrence of enteritis, and protecting the whole intestine from radiation-induced gut injury remains an unmet clinical need. Circulating extracellular vesicles (EVs) are proven to be vital factors in the establishment of tissue and cell microenvironments. In this study, we aimed to investigate a radioprotective strategy mediated by small EVs (exosomes) in the context of irradiation-induced intestinal injury. We found that exosomes derived from donor mice exposed to total body irradiation (TBI) could protect recipient mice against TBI-induced lethality and alleviate radiation-induced gastrointestinal (GI) tract toxicity. To enhance the protective effect of EVs, profilings of mouse and human exosomal microRNAs (miRNAs) were performed to identify the functional molecule in exosomes. We found that miRNA-142-5p was highly expressed in exosomes from both donor mice exposed to TBI and patients after radiotherapy (RT). Moreover, miR-142 protected intestinal epithelial cells from irradiation-induced apoptosis and death and mediated EV protection against radiation enteritis by ameliorating the intestinal microenvironment. Then, biomodification of EVs was accomplished via enhancing miR-142 expression and intestinal specificity of exosomes, and thus improved EV-mediated protection from radiation enteritis. Our findings provide an effective approach for protecting against GI syndrome in people exposed to irradiation.

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BACKGROUND: Multikinase inhibitors (MKIs) treatment has been proven as a powerful strategy in cancer therapy. However, it is greatly hampered by its common adverse effect known as hand-foot skin reaction (HFSR), especially in patients with moderate-to-severe HFSR. OBJECTIVE: To investigate the clinical characteristics, histopathological features, treatment response, and bio-indicators of HFSR. METHODS: We retrospectively reviewed the medical records of 102 patients with moderate-to-severe HFSR resulting from MKIs therapy. RESULTS: The median time to development of moderate-to-severe HFSR was 18 days, which would be significantly affected by the type of MKIs and the history of HFSR. Notably, we found that HFSR was classified into three consecutive stages: erythematous lesion, yellow hyperkeratotic lesion with surrounding erythema, and hyperkeratotic lesion. Inflammation was observed in the first two stages of HFSR, but disappeared in the third stage; in contrast, the hyperkeratosis gradually became thicker from stage one to stage three. Moreover, topical medications were demonstrated as an effective therapy for HFSR, among which, the topical steroids and urea ointment treatment response rate was 37.14%, the Shouzu Ning Decoction (SND) treatment response rate was 65%, and the SND in combination with urea ointment treatment response rate was 75%, meanwhile, systemic therapies did not improve the therapeutic efficacy of topical medications alone. In addition, the serum levels of HMGB1 were found to be a potential indicator for tracking the healing process as well as predicting the prognosis of HFSR. CONCLUSION: This study revealed the potential factors affecting the development of HFSR, evaluated the therapeutic response towards different strategies for treating HFSR, and identified a potential prognostic indicator of HFSR.

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The development of new catalysts with high selectivity and efficiency for the electrocatalytic nitrate reduction reaction (NtRR) to produce ammonia (NH3) at room temperature and ambient pressure is still a challenge. Herein, we report a simple in situ growth method for the controlled synthesis of a GDY-MnOx heterointerface by selectively anchoring and growing MnOx on GDY surfaces. Experimental results show that the incomplete charge-transfer between GDY and Mn atoms at the interface structures largely increases the number of active sites, improves the electrical conductivity, and therefore results in excellent electrocatalytic performance for NH3 synthesis with a maximum FE of 95.4%, an NH3 yield rate of 463.4 µmol h-1 cm-2 and high long-term stability in 0.1 M KOH + 0.1 M NO3- aqueous electrolytes at room temperature and ambient pressure.

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Purpose: To evaluate the effects of dentin pretreatment with chitosan-loaded oleuropein nanoparticles (CONPs) on the durability of resin-dentin bonding interfaces. Methods: Eighty freshly extracted non-carious human third molars were randomly divided into four groups (n = 20 each): a de-ionized water (DW) group, a chitosan (CS) group, a chlorhexidine (CHX) group and a CONP group. The dentin in the DW, CS, CHX, and CONP groups were pretreated with de-ionized water, 1.0 mg/L CS solution, 2% chlorhexidine solution, and CONP suspension (prepared with 100 mg/L oleuropein), respectively, followed by the universal adhesive and resin composites. The bonded teeth of each group were randomly divided into two subgroups: an immediate subgroup and an aged subgroup. The bonded teeth of each group were then cut into the bonded beams. We measured their microtensile bond strength (µTBS), observed the characteristics of bonding interface by atomic force microscope, calculated the percentage of silver particles in a selected area for interfacial nanoleakage analysis, and evaluated the endogenous gelatinase activity within the bonding interface for in-situ zymogram analysis. Data were analyzed with two-way ANOVA and LSD multiple comparison test (P < 0.05). Results: Regardless of after 24 h or after thermocycling, CONP exhibited better µTBS (P < 0.05) than the other three groups except that there was not a statistical significance (P > 0.05) in the CONP and CHX groups after 24 h. Besides, the CONP group presented significantly higher modulus of elasticity in the hybrid layers (P < 0.05), lower expression of nanoleakage (P < 0.05), and better inhibitory effect of matrix metalloproteinases than the other three groups before and after thermocycling. Conclusion: Altogether, the CONPs had the potential to act as a dentin primer, which could effectively improve the dentin-resin binding durability.

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BACKGROUND: The integrity and stability of collagen are crucial for the dentin structure and bonding strength at dentin-resin interface. Natural plant-derived polypehenols have been used as collagen crosslinkers. OBJECTIVE: The aims of the study were to develop novel chitosan oleuropein nanoparticles (CS-OL-NPs), and to investigate the CS-OL-NPs treated dentin's the resistance to enzymatic degradation and mechanic property. METHODS: CS-OL-NPs were developed using the ionotropic gelation method. Release and biocompatibility of the CS-OL-NPs were tested. Twenty demineralized dentin collage specimens were randomized into four interventions groups: A, Deionized Water (DW); B, 5% glutaraldehyde solution (GA); C, 1 mg/ml chitosan (CS); and D, 100 mg/L CS-OL-NPs. After 1-min interventions, dentin matrix were evaluated by the micro-Raman spectroscopy for the modulus of elasticity test. Collagen degradation was assessed using hydroxyproline (HYP) assay. RESULTS: CS-OL-NPs were spherical core-shape with a size of 161.29 ± 8.19 nm and Zeta potential of 19.53 ± 0.26 mV. After a burst release of oleuropein in the initial 6 h, there was a long-lasting steady slow release. CS-OL-NPs showed a good biocompatibility for the hPDLSCs. The modulus of elasticity in the crosslinked groups were significantly higher than that in the control group (P< 0.05 for all). The specimens treated with CS-OL-NP showed a greater modulus of elasticity than those treated with GA and CS (P< 0.05 for both). The release of HYP in the crosslinked group was significantly lower than that in the non-crosslinked groups (P< 0.05 for all). CONCLUSION: CS-OL-NPs enhanced the dentin mechanical property and resistance to biodegradation, with biocompatibility and potential for clinical application.

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Carbon materials derived from metal-organic frameworks have attracted increasing attention as anodes for energy storage. In this study, Fe, Ni-doped ZIF-8 is carbonized at high temperature to obtain bimetallic Fe and Ni modified tension -relaxed carbon (FeNi@trC). Fe and Ni have opposite structural modification effects when the metal ions are doped into the ZIF-8 dodecahedron. The obtained carbon material maintains the regular dodecahedron morphology, which means the relaxation of tension and strong thermal stability during annealing. Moreover, the presence of nickel enhances the carbonization degree and electrochemical stability of FeNi@trC, while the calcination of the tensive ZIF-8 precursor offers more defect sites. The discharge capacities of FeNi@trC materials are stable at 182.9 mAh·g-1and 567.9 mAh·g-1for sodium-ion batterie (SIB) and lithium-ion batterie (LIB) at 0.05 A·g-1. Compared with the current density of 0.05 A·g-1, the discharge capacity of SIB and LIB attenuates by 29.4% and 55.9% at 1 A·g-1, respectively, and the FeNi@trC shows good performance stability in the following cycles.

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Background: Precision cancer medicine-related rashes are a kind of skin and mucous lesions caused by precision therapy. More and more evidences indicated that such events should not be ignored in the course of anti-tumor therapy. Since cancer treatment entered the "Precision Era", there has been a rapid increase in this field. However, there was few bibliometric studies to provide an overall review of this field. This study aims to evaluate the literature output and trends in researches on precision cancer medicine-related rashes from a global perspective. Methods: Collected publications on precision cancer medicine-related rashes from the Web of Science Core Collection database, which were limited to articles and reviews in English. Microsoft Excel, VOS viewer and CiteSpace V were used for quantitative and visual analysis. Results: A total of 1,229 papers were identified. From 2008 to 2021, annual publications increased year by year. The United States published the most papers in this field (44.9%) and ranking first in citation frequency (19,854 times) and H-index (69). The University of Texas system ranks first with 98 papers published. Lacouture M.E and Robert C were the principal investigators. Cancers has the largest number of articles published, with 70 articles. In recent years, there have been research hotspots related to immunotherapy, including ipilimumab, immunotherapy, tumor microenvironment, association, checkpoint inhibitor, and cutaneous adverse event. Conclusion: Precision cancer medicine-related rashes are a hot research topic in oncology. The number of relevant publications will increase dramatically. "Checkpoint inhibitors", "skin adverse events", "associations" and "tumor microenvironment" may become research hotspots in the future.

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Effective and rapid capture of heavy metal oxo-anions from wastewater is a fascinating research topic, but it remains a great challenge. Herein, benzimidazole and -CH3 groups were integrated into UiO-66 in succession via a step-by-step linker modification strategy that was performed by presynthesis modification (to give Bim-UiO-66) and subsequently by postsynthetic ionization (to give Bim-UiO-66-Me). The UiO-66s (UiO-66, Bim-UiO-66, and Bim-UiO-66-Me) were applied in the removal of heavy metal oxo-anions from water. The two benzimidazole derivatives (Bim-UiO-66 and Bim-UiO-66-Me) showed much better performance than UiO-66, as both the initial sorption rate and sorption capacities decreased in the order Bim-UiO-66-Me > Bim-UiO-66 > UiO-66. The maximum performances of Bim-UiO-66 are 5.1 and 1.7 times those of UiO-66. Remarkably, Bim-UiO-66-Me shows 7.5 and 3.0 times better performance than UiO-66. The higher absorptivity of cationic Bim-UiO-66-Me compared with UiO-66 can be attributed to a strong Coulombic interaction as well as an anion-π interaction and hydrogen bonding between the benzimidazolium functional group and heavy metal oxo-anions. The as-synthesized Bim-UiO-66-Me not only provides a promising candidate for application in removal of heavy metal oxo-anions in wastewater treatment but also opens up a new strategy for the design of high-performance adsorbents.

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Sodium ion batteries (SIBs) are expected to replace lithium ion batteries (LIBs) as the next generation of large-scale energy storage applications because of their superior cost performance. However, the larger ionic radius of Na+ causes a remarkable volume expansion than that of Li+ during charge and discharge, which reduces the performance of the battery. In this work, we engineered a composite material in that monodispersed 2 nm Sb2S3 particles are uniformly loaded into a carbon matrix (Sb2S3/CZM), which is obtained by carbonization of a zirconium-based MOF with adsorption of Sb. The obtained composite material has a high specific surface area in favor of mass transfer, and the porous structure can resist many volume changes in the circulation process. Moreover, the ultrafine Sb2S3 particles are well-distributed in the composite material, which increases the utilization of the active substance and is promising for the storage of Na+. Based on its unique structure, the Sb2S3/CZM composite shows a specific capacity of 550 mA h g-1 at 100 mA g-1 and an excellent cycling stability of 88.9% retention after 1000 cycles at 3 A g-1. The excellent electrochemical performance provides enlightenment for the rational design of hierarchical heterostructures for energy storage applications.