Nanostructured oxides find multiple uses in a diverse range of applications including catalysis, energy storage, and environmental management, their higher surface areas, and, in some cases, electronic properties resulting in different physical properties from their bulk counterparts. Developing structure-property relations for these materials requires a determination of surface and subsurface structure. Although microscopy plays a critical role owing to the fact that the volumes sampled by such techniques may not be representative of the whole sample, complementary characterization methods are urgently required. We develop a simple nuclear magnetic resonance (NMR) strategy to detect the first few layers of a nanomaterial, demonstrating the approach with technologically relevant ceria nanoparticles. We show that the 17O resonances arising from the first to third surface layer oxygen ions, hydroxyl sites, and oxygen species near vacancies can be distinguished from the oxygen ions in the bulk, with higher-frequency 17O chemical shifts being observed for the lower coordinated surface sites. H217O can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. 17O NMR spectra of thermally treated nanosized ceria clearly show how different oxygen species interconvert at elevated temperature. Density functional theory calculations confirm the assignments and reveal a strong dependence of chemical shift on the nature of the surface. These results open up new strategies for characterizing nanostructured oxides and their applications.

A set of 316 modern surface pollen samples, sampling all the alpine vegetation types that occur on the Tibetan Plateau, has been compiled and analysed. Between 82 and 92% of the pollen present in these samples is derived from only 28 major taxa. These 28 taxa include examples of both tree (AP) and herb (NAP) pollen types.  Most of the modern surface pollen samples accurately reflect the composition of the modern vegetation in the sampling region. However, airborne dust‐trap pollen samples do not provide a reliable assessment of the modern vegetation. Dust‐trap samples contain much higher percentages of tree pollen than non‐dust‐trap samples, and many of the taxa present are exotic. In the extremely windy environments of the Tibetan Plateau, contamination of dust‐trap samples by long‐distance transport of exotic pollen is a serious problem.  The most characteristic vegetation types present on the Tibetan Plateau are alpine meadows, steppe and desert. Non‐arboreal pollen (NAP) therefore dominates the pollen samples in most regions. Percentages of arboreal pollen (AP) are high in samples from the southern and eastern Tibetan Plateau, where alpine forests are an important component of the vegetation. The relative importance of forest and non‐forest vegetation across the Plateau clearly follows climatic gradients: forests occur on the southern and eastern margins of the Plateau, supported by the penetration of moisture‐bearing airmasses associated with the Indian and Pacific summer monsoons; open, treeless vegetation is dominant in the interior and northern margins of the Plateau, far from these moisture sources.  The different types of non‐forest vegetation are characterized by different modern pollen assemblages. Thus, alpine deserts are characterized by high percentages of Chenopodiaceae and Artemisia, with Ephedra and Nitraria. Alpine meadows are characterized by high percentages of Cyperaceae and Artemisia, with Ranunculaceae and Polygonaceae. Alpine steppe is characterized by high abundances of Artemisia, with Compositae, Cruciferae and Chenopodiaceae. Although Artemisia is a common component of all non‐forest vegetation types on the Tibetan Plateau, the presence of other taxa makes it possible to discriminate between the different vegetation types.  The good agreement between modern vegetation and modern surface pollen samples across the Tibetan Plateau provides a measure of the reliability of using pollen data to reconstruct past vegetation patterns in non‐forested areas.

Cisplatin (DDP) was reported to improve pathological complete response (pCR) rates in triple-negative breast cancer (TNBC) patients, however, the molecular mechanism still remains largely unknown. Emerging evidence suggested that some chemotherapeutic drugs played anti-tumor effects by inducing cell pyroptosis. Nevertheless, whether pyroptosis contributes to the DDP-induced anti-tumor effect in TNBC remains unexploited. In the present study, NLRP3/caspase-1/GSDMD pyroptosis pathway was involved in the DDP-induced anti-tumor effect of TNBC in vitro and in vivo , providing evidence that DDP might induce pyroptosis in TNBC. Moreover, DDP activated NLRP3/caspase-1/GSDMD pyroptosis pathway by up-regulating the long non-coding RNA (lncRNA) maternally expressed gene 3 (MEG3). Furthermore, knockdown of MEG3 not only partly abolished the activation effect of DDP on NLRP3/caspase-1/GSDMD pathway-mediated pyroptosis, but also reversed the suppression of DDP on tumor growth and metastasis ability in vitro and in vivo, further confirming that MEG3 may partially mediate the pyroptotic signaling upon DDP treatment. Thus, our data uncovered a novel mechanism that DDP induced pyroptosis via activation of MEG3/NLRP3/caspase-1/GSDMD pathway in TNBC to exert anti-tumor effects, which may help to develop new strategies for the therapeutic interventions in TNBC.

Facet engineering of oxide nanocrystals represents a powerful method for generating diverse properties for practical and innovative applications. Therefore, it is crucial to determine the nature of the exposed facets of oxides in order to develop the facet/morphology–property relationships and rationally design nanostructures with desired properties. Despite the extensive applications of electron microscopy for visualizing the facet structure of nanocrystals, the volumes sampled by such techniques are very small and may not be representative of the whole sample. Here, we develop a convenient 17O nuclear magnetic resonance (NMR) strategy to distinguish oxide nanocrystals exposing different facets. In combination with density functional theory calculations, we show that the oxygen ions on the exposed (001) and (101) facets of anatase titania nanocrystals have distinct 17O NMR shifts, which are sensitive to surface reconstruction and the nature of the steps on the surface. The results presented here open up methods for characterizing faceted nanocrystalline oxides and related materials.

Gaseous oxides generated during industrial processes, such as carbon oxides (CO x ) and nitrogen oxides (NO x ), have important effects on the Earth’s atmosphere. It is highly desired to develop a low-cost and efficient route to convert them to harmless products. Here, direct splitting of gaseous oxides was proposed on the basis of photocatalysis by an amorphous oxide semiconductor. As an example, splitting of CO2 into carbon and oxygen was achieved over amorphous zinc germanate (α-Zn-Ge-O) semiconductor photocatalyst under 300 W Xe lamp irradiation. Electron paramagnetic resonance and 18O isotope labeling indicated that the splitting of CO2 was achieved via photoinduced oxygen vacancies on α-Zn-Ge-O reacting and thus filling with O of CO2, while the photogenerated electrons reduced the carbon species of CO2 to solid carbon. Under irradiation, such a defect reaction is sustainable by continuous photogenerated hole oxidation of surface oxygen atoms on α-Zn-Ge-O to form oxygen vacancies and to release O2. When we used H2O or NO in place of CO2, H2 and O2 or N2 and O2 were evolved, respectively, indicating the same mechanism can also split H2O or NO.