Zeolite-encapsulated metal clusters have been shown to be an effective bifunctional catalyst for tandem catalysis. Nevertheless, the efficient encapsulation of nanometric metal species into a high-aluminum ZSM-5 zeolite still poses a significant challenge. In this contribution, we have prepared well-dispersed and ultra-small Ru clusters encapsulated within a high-aluminum ZSM-5 zeolite (with a Si/Al ratio of ∼30–40) via an in situ two-stage hydrothermal synthesis method. Small Ru clusters with an average size of ∼1 nm have been identified by scanning transmission electron microscopy and hydrogen chemisorption. Shape-selective hydrogenation experiments with different probe molecules reveal a predominant encapsulation (∼90%) of metal clusters within the MFI zeolite cavities, which significantly enhances thermal stability of metal clusters against sintering. 27Al magic angle spinning nuclear magnetic resonance and Brønsted acid site (BAS) titration experiments show the successful incorporation of aluminum species (>99%) into the zeolite framework and build-up of intimacy between the Ru clusters and BASs at a sub-nanometric level. The resulting Ru@H-ZSM-5 shows an enhanced activity and stability for the crucial hydrodeoxygenation (HDO) of phenol to cyclohexane, in biomass valorization. This synthesis strategy could be of great help for the rational design and development of zeolitic bifunctional catalysts and could be extended to other crystalline porous materials.

Liquid-phase hydrodeoxygenation (HDO), catalyzed by metal or metal-acid sites, provides an effective catalytic strategy to remove oxygen-containing functionalities of lignin-derived phenolic compounds on the route to fuels and chemicals. Developing the catalyst with high activity and stability is crucial for such a chemical process but still remains a significant challenge. In this contribution, highly dispersed subnanometric Ru metal clusters (<1.5 nm) encapsulated in the cavities of MWW zeolites, including HMCM-22 and its siliceous analog ITQ-1, have been developed for the HDO of guaiacol, an important lignin-derived phenolic monomer, in an apolar liquid phase under mild conditions (160 °C, 3 MPa H 2 ). We validate the effective encapsulation of Ru metal clusters in ITQ-1 and HMCM-22 zeolite cavities via complementary characterization methods. The detailed reaction pathways of the HDO of guaiacol are depicted by using guaiacol, phenol, and anisole as reactants. The subnanometric Ru metal clusters confined in MWW zeolite thin layers (20−30 nm in thickness) show remarkable enhancement in HDO activity compared to the large metal particles. The close proximity between Ru metal clusters and Brønsted acid sites (BAS) confined in zeolite constraints delivers a synergistic effect, leading to an additional enhancement in catalytic activity as well as product selectivity. The super stability of the ultrafine Ru metal clusters against sintering and leaching after successive catalytic runs is achieved. The welldefined mono-or bifunctional Ru-containing MWW zeolite catalysts enable the fundamental understanding of HDO of ligninderived phenolic compounds in the apolar liquid phase and also provide a prototype for the design of superior catalysts for other energy-related transformations.

Russula vinosa Lindbl is a wild edible mushroom that is usually used for original material of food and soup and has rich nutritional value. What are the nutritional ingredients? In order to answer this question, we investigated the chemical constituents of this wild functional food. Six new compounds (1–6), together with nine known ones (7–15), were isolated from R. vinosa. The six new compounds were named as vinosane (1), rulepidadione C (2), (24E)-3,4-seco-cucurbita-4,24-diene-26,29-dioic acid-3-methyl ester (3), (24E)-3,4-seco-cucurbita-4,24-diene-26-oic acid-3-ethyl ester (4), (24E)-3β-hydroxycucurbita-5,24-diene-26,29-dioic acid (5), and (2S,3S,4R,2′R)-2-(2′-hydroxydocosanoylamino)eicosane-1,3,4-triol (6). Their structures were determined based on spectroscopic methods including HR-ESI-MS, 1D, and 2D NMR. Moreover, a cell counting kit-8 (CCK-8 kit) was used to screen for the cytotoxicity of compounds 1–5 and 7–13 on mouse macrophage RAW 264.7 cells. The results showed that compounds 1–5 and 7–13 had no obvious cytotoxicity. In addition, the inhibitory effects on nitric oxide (NO) production in lipopolysaccharide (LPS)-activated mouse macrophage RAW 264.7 cells were evaluated. Compounds 1, 3, 4, 7, 12, and 13 showed moderate inhibitory activity on NO production.