Hepatic artery infusion chemotherapy combined with camrelizumab plus rivoceranib for hepatocellular carcinoma with portal vein tumor thrombosis: a multicenter propensity score-matching analysis.

BACKGROUND: Portal vein tumor thrombosis (PVTT) signifies late-stage hepatocellular carcinoma (HCC) with high-risk progression and poor prognosis. As a standard treatment, sorafenib monotherapy has limited the efficacy in managing HCC with PVTT. Currently, both hepatic arterial infusion chemotherapy (HAIC) and the combination of camrelizumab and rivoceranib have shown favorable survival benefits for advanced HCC, surpassing the standard sorafenib treatment. In this study, we investigate the safety and efficacy of HAIC combined with camrelizumab and rivoceranib in treating HCC patients with PVTT. METHODS: From January 2020 to December 2021, HCC patients with PVTT, who received either a triple regime of HAIC combined with camrelizumab and rivoceranib or a dual regime of camrelizumab and rivoceranib as their first-line treatment, were reviewed for eligibility at four hospital centers in China. To balance any intergroup differences, propensity score matching (PSM) was applied. The aim of this study is to compare the efficacy of the dual and triple combination treatment regimens based on survival prognosis and tumor response and evaluate the safety based on the occurrence of adverse reactions. RESULT: In this study, a total of 411 patients who received either the triple treatment regime (HAIC combined with camrelizumab plus rivoceranib, referred to as the HAICCR group, n = 292) or the dual treatment regime (camrelizumab combined with rivoceranib, referred to as the CR group, n = 119) between January 2020 and December 2021 were included. The results showed that the HAICCR group exhibited significantly better overall survival (mOS: 19.60 months vs. 11.50 months, p < 0.0001) and progression-free survival (mPFS: 10.0 months vs. 5.6 months, p < 0.0001) compared to the CR group in the overall cohort. Moreover, the HAICCR group also had a significantly higher ORR (objective response rate, 55.5% vs. 42.0%, p = 0.013) and DCR (disease control rate, 89.0% vs. 79.0%) compared to the CR group. After PSM, a final matched cohort of 83 pairs was obtained, and the survival benefits were consistent in this cohort as well (mOS: 18.70 months vs. 11.0 months, p < 0.0001; mPFS: 10.0 months vs. 5.6 months, p < 0.0001). However, there was no significant difference in the ORR between the triple and dual combination regimes. Univariate and multivariate analysis showed that CTP (Child-Turcotte-Pugh) stage, ALBI (albumin-bilirubin index) grade, tumor number, and treatment regime were significant risk factors affecting overall survival, while AFP (α-fetoprotein) level, tumor number, metastasis, and treatment regime were significant risk factors affecting progression-free survival. As for safety, hypertension and hand-foot syndrome were the two most common adverse reactions in both groups, with no significant difference in the occurrence of adverse reactions between the two groups (p < 0.05). CONCLUSION: In the context of advanced HCC patients with PVTT, the combination regime of HAIC and camrelizumab plus rivoceranib demonstrates more excellent capacity for prolonging survival and offers a well-tolerated safety compared to the CR dual therapy approach. This triple regime represents a therapeutic modality of broad prospects and vast potential for HCC patients with PVTT.

Renal interstitial fibrotic assessment using non-Gaussian diffusion kurtosis imaging in a rat model of hyperuricemia.

BACKGROUND: To investigate the feasibility of Diffusion Kurtosis Imaging (DKI) in assessing renal interstitial fibrosis induced by hyperuricemia. METHODS: A hyperuricemia rat model was established, and the rats were randomly split into the hyperuricemia (HUA), allopurinol (AP), and AP + empagliflozin (AP + EM) groups (n = 19 per group). Also, the normal rats were selected as controls (CON, n = 19). DKI was performed before treatment (baseline) and on days 1, 3, 5, 7, and 9 days after treatment. The DKI indicators, including mean kurtosis (MK), fractional anisotropy (FA), and mean diffusivity (MD) of the cortex (CO), outer stripe of the outer medulla (OS), and inner stripe of the outer medulla (IS) were acquired. Additionally, hematoxylin and eosin (H&E) staining, Masson trichrome staining, and nuclear factor kappa B (NF-κB) immunostaining were used to reveal renal histopathological changes at baseline, 1, 5, and 9 days after treatment. RESULTS: The HUA, AP, and AP + EM group MKOS and MKIS values gradually increased during this study. The HUA group exhibited the highest MK value in outer medulla. Except for the CON group, all the groups showed a decreasing trend in the FA and MD values of outer medulla. The HUA group exhibited the lowest FA and MD values. The MKOS and MKIS values were positively correlated with Masson's trichrome staining results (r = 0.687, P < 0.001 and r = 0.604, P = 0.001, respectively). The MDOS and FAIS were negatively correlated with Masson's trichrome staining (r = -626, P < 0.0014 and r = -0.468, P = 0.01, respectively). CONCLUSION: DKI may be a non-invasive method for monitoring renal interstitial fibrosis induced by hyperuricemia.

Vinyl-Group-Anchored Covalent Organic Framework for Promoting the Photocatalytic Generation of Hydrogen Peroxide.

The artificial photosynthesis of H2O2 from water and oxygen using semiconductor photocatalysts is attracting increasing levels of attention owing to its green, environmentally friendly, and energy-saving characteristics. Although covalent organic frameworks (COFs) are promising materials for promoting photocatalytic H2O2 production owing to their structural and functional diversity, they typically suffer from low charge-generation and -transfer efficiencies as well as rapid charge recombination, which restricts their use as catalysts for photocatalytic H2O2 production. Herein, we report a strategy for anchoring vinyl moieties to a COF skeleton to facilitate charge separation and migration, thereby promoting photocatalytic H2O2 generation. This vinyl-group-bearing COF photocatalyst exhibits a H2O2-production rate of 84.5 µmol h-1 (per 10 mg), which is ten-times higher than that of the analog devoid of vinyl functionality and superior to most reported COF photocatalysts. Both experimental and theoretical studies provide deep insight into the origin of the improved photocatalytic performance. These findings are expected to facilitate the rational design and modification of organic semiconductors for use in photocatalytic applications.

Alkyl sulfonate surfactant mediates electroreduction of carbon dioxide to ethylene or ethanol over hydroxide-derived copper catalysts.

For CO2 electroreduction (CO2ER) to C2 compounds, it is generally accepted that the formation of ethylene and ethanol shares the same intermediate, *HCCOH. The majority of studies have achieved high faradaic efficiency (FE) towards ethylene, but faced challenges to get high ethanol FE. Herein, we present an alkyl sulfonate surfactant (e.g., sodium dodecyl sulfonate, SDS) mediated CO2ER to a C2 product over an in situ generated Cu catalyst (Cu@SDS) from SDS-modified Cu(OH)2. It achieves the CO2ER to ethylene as the sole C2 product at low applied voltages with a FE of 55% at -0.6 V vs. RHE and to ethanol as the main product at potentials ≥0.7 V with a maximum FE of 64% and a total C2 FE of 86% at -0.8 V, with a current density of 231 mA cm-2 in a flow cell. Mechanism investigation indicates that SDS modifies the oxidation state of the in situ formed Cu species in Cu@SDS, thus tuning the catalyst activity for CO2ER and lowering the C-C coupling energy barrier; meanwhile, it tunes the adsorption mode of the *HCCOH intermediates on the catalyst, thus mediating the selectivity of CO2ER towards C2 products.

Polyarene Oxides with Tunable Quinone Units for Photocatalytic CO2 Reduction: A Simple Strategy toward Effective and Selective Catalysts.

The photocatalytic transformation of carbon dioxide (CO2) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA). The resultant PAOs show tunable D-A structures and electronic band positions depending on the degree of oxidation, which can catalyze the photoreduction of CO2 with water under visible light irradiation, generating CO as the sole carbonaceous product without H2 generation. Especially, the PAO with an oxygen content of 17.6% afforded the highest CO production rate of 161.9 µmol g-1 h-1. It is verified that the redox transformation between quinone and phenolic hydroxyl in PAOs achieves CO2 photoreduction coupled with water oxidation. This study provides a facile way to access conjugated polymers with a tunable D-A structure and demonstrates that the resultant PAOs are promising photocatalysts for CO2 reduction.

Development of macrophage-associated genes prognostic signature predicts clinical outcome and immune infiltration for sepsis.

Sepsis is a major global health problem, causing a significant burden of disease and death worldwide. Risk stratification of sepsis patients, identification of severe patients and timely initiation of treatment can effectively improve the prognosis of sepsis patients. We procured gene expression datasets for sepsis (GSE54514, GSE65682, GSE95233) from the Gene Expression Omnibus and performed normalization to mitigate batch effects. Subsequently, we applied weighted gene co-expression network analysis to categorize genes into modules that exhibit correlation with macrophage activity. To pinpoint macrophage-associated genes (MAAGs), we executed differential expression analysis and single sample gene set enrichment analysis. We then established a prognostic model derived from four MAAGs that were significantly differentially expressed. Functional enrichment analysis and immune infiltration assessments were instrumental in deciphering the biological mechanisms involved. Furthermore, we employed principal component analysis and conducted survival outcome analyses to delineate molecular subgroups within sepsis. Four novel MAAGs-CD160, CX3CR1, DENND2D, and FAM43A-were validated and used to create a prognostic model. Subgroup classification revealed distinct molecular profiles and a correlation with 28-day survival outcomes. The MAAGs risk score was developed through univariate Cox, LASSO, and multivariate Cox analyses to predict patient prognosis. Validation of the risk score upheld its prognostic significance. Functional enrichment implicated ribonucleoprotein complex biogenesis, mitochondrial matrix, and transcription coregulator activity in sepsis, with an immune infiltration analysis indicating an association between MAAGs risk score and immune cell populations. The four MAAGs exhibited strong diagnostic capabilities for sepsis. The research successfully developed a MAAG-based prognostic model for sepsis, demonstrating that such genes can significantly stratify risk and reflect immune status. Although in-depth mechanistic studies are needed, these findings propose novel targets for therapy and provide a foundation for future precise clinical sepsis management.

A general strategy for recycling polyester wastes into carboxylic acids and hydrocarbons.

Chemical recycling of plastic wastes is of great significance for sustainable development, which also represents a largely untapped opportunity for the synthesis of value-added chemicals. Herein, we report a novel and general strategy to degrade polyesters via directly breaking the Calkoxy-O bond by nucleophilic substitution of halide anion of ionic liquids under mild conditions. Combined with hydrogenation over Pd/C, 1-butyl-2,3-dimethylimidazolium bromide can realize the deconstruction of various polyesters including aromatic and aliphatic ones, copolyesters and polyester mixtures into corresponding carboxylic acids and alkanes; meanwhile, tetrabutylphosphonium bromide can also achieve direct decomposition of the polyesters with ß-H into carboxylic acids and alkenes under hydrogen- and metal-free conditions. It is found that the hydrogen-bonding interaction between ionic liquid and ester group in polyester enhances the nucleophilicity of halide anion and activates the Calkoxy-O bond. The findings demonstrate how polyester wastes can be a viable feedstock for the production of carboxylic acids and hydrocarbons.

Partially Nitrided Ni Nanoclusters Achieve Energy-Efficient Electrocatalytic CO2 Reduction to CO at Ultralow Overpotential.

Electrocatalytic CO2 reduction reaction (CO2 RR) offers a promising strategy to lower CO2 emission while producing value-added chemicals. A great challenge facing CO2 RR is how to improve energy efficiency by reducing overpotentials. Herein, partially nitrided Ni nanoclusters (NiNx ) immobilized on N-doped carbon nanotubes (NCNT) for CO2 RR are reported, which achieves the lowest onset overpotential of 16 mV for CO2 -to-CO and the highest cathode energy efficiency of 86.9% with CO Faraday efficiency >99.0% to date. Interestingly, NiNx /NCNT affords a CO generation rate of 43.0 mol g-1  h-1 at a low potential of -0.572 V (vs RHE). DFT calculations reveal that the NiNx nanoclusters favor *COOH formation with lower Gibbs free energy than isolated Ni single-atom, hence lowering CO2 RR overpotential. As NiNx /NCNT is applied to a membrane electrode assembly system coupled with oxygen evolution reaction, a cell voltage of only 2.13 V is required to reach 100 mA cm-2 , with total energy efficiency of 62.2%.

Tuning d-Band Structure of CuII in Coordinated Polymer via d-π Conjugation for Improving CO2 Electroreduction Selectivity toward C2 Products.

Copper-coordinated catalysts are reported to be effective for electrocatalytic CO2 reduction reaction (CO2 RR) to C2 products but suffer from low selectivity. Herein a strategy was developed to tune the d-band structure of CuII via coordinating with aromatic ligands to form Cu-based conjugated polymers for CO2 RR to C2 chemicals. The catalysts derived from copper chloride coordinating with tetraminobenzoquinone (TABQ) and with 1,2,4,5-benzenetetramine possessed high-density and compact Cu single-atom sites and displayed high activity for CO2 RR to C2 products. Especially, Cu-TABQ exhibited a maximum C2 faradaic efficiency of 63.2 % with a current density of 423 mA cm-2 at -1.17 V (vs. reversible hydrogen electrode). Density functional theory calculations indicated that the TABQ linker possessing C=O groups significantly widened the d-band of coordinated CuII , which facilitated binding of *CO intermediate on the catalyst and thus enhanced C-C coupling. This work provides mechanistic insight into the CuII -coordinated polymers for CO2 RR with high selectivity toward C2 products.

Carbazolic Conjugated Organic Polymers for Visible-Light-Driven CO2 Photoreduction with H2 O to CO with High Efficiency and Selectivity.

Visible-light-driven CO2 photoreduction with H2 O to value-added chemicals in high efficiency and selectivity is significant but challenging. Herein, a series of carbazolic conjugated organic polymers (CB-COPs) with electron donor-acceptor (D-A) structures were prepared, which showed high efficiency for visible-light-driven photocatalytic reduction of CO2 with H2 O in a solid-gas mode, affording CO as the exclusive carbonaceous product. Especially, CB-COP-mpd derived from 3,5-di(9H-carbazol-9-yl)pyridine exhibited the highest CO evolution rate up to 191.46 µmol g-1 h-1 with a selectivity of 100 %. Mechanism studies showed that carbazolyl is a promising electron donor candidate for constructing CB-COPs with D-A structures, capable of improving the catalytic efficiency and suppressing H2 generation. The acceptor building block with excessive electron withdrawing capability was favorable to H2 O adsorption, thus resulting in the generation of H2 . This work provides new insights for designing COPs photocatalysts for CO2 photocatalytic reduction.

Interface engineered Co, Ni, Fe, Cu oxide hybrids with biphasic structures for water splitting with enhanced activity.

Developing high-performance catalysts for water splitting via renewable electricity is of great significance for the clean production of hydrogen. This work reports rational design and controllable fabrication of metal oxide hybrid catalyst CoNiFe2O5·2CuO with unique biphasic microstructures for electrochemical water splitting. Benefited from the presence of CuO nanoparticles as the second phase, more defects and active sites were formed around the interfaces of CoNiFe2O5 and CuO, which led to excellent performances for electrocatalytic water splitting. In particular, the catalyst exhibited outstanding activity for hydrogen evolution reaction with a small overpotential of 30 mV to reach a current density of 10 mA cm-2 and showed a higher turnover frequency (0.3 s-1) than commercial catalyst Pt/C (0.1 s-1) under an overpotential of 50 mV. Moreover, it also displayed good activity for oxygen evolution reaction with an overpotential of 264 mV at 10 mA cm-2. Using CoNiFe2O5·2CuO as the catalyst for electrode pair to construct a cell, a very low cell voltage of 1.53 V is enough to achieve overall water splitting at 10 mA cm-2 in 1 M KOH electrolyte, and the cell could maintain the stable performance at 10 mA cm-2 within 100 h. The as-prepared metal oxide hybrids with biphasic microstructures may have promising application potentials in water splitting.

Cobalt Carbonate-Coated Nitrogen-Doped Carbon Nanotubes with a Sea-Cucumber Morphology for Electrocatalytic Water Splitting.

Herein, we report CoCO3-coated nitrogen-doped carbon nanotubes (NCNTs) with a sea cucumber-like morphology for water splitting. The sample with a CoCO3 content of 26.8 wt % (CoCO3/NCNT-1) exhibits excellent performance for the hydrogen evolution reaction in 1.0 M KOH electrolyte with an overpotential of 58 mV to reach 10 mA cm-2, better than the most non-noble metal catalysts reported; meanwhile, it exhibits superior electrocatalytic activity for the oxygen evolution reaction. The excellent performance of the catalyst is attributed to the nanotip effect caused by the sea-cucumber-like morphology. Notably, CoCO3/NCNT-1 can attain turnover frequencies of 2.7 s-1 at an overpotential of 50 mV, higher than that of Pt/C (1.5 s-1). A cell constructed using CoCO3/NCNT-1 as the catalyst of the electrode pair needs a low cell voltage of 1.54 V at 10 mA cm-2, superior to most reported cells. In addition, CoCO3/NCNT-1 can maintain 10 mA cm-2 for overall water splitting for 100 h without activity loss.

Screening and Identification of Trichoderma Strains isolated from Natural Habitats in China with Potential Agricultural Applications.

Trichoderma spp. are widely distributed in natural habitats and have been evaluated as a potential biocontrol agent (BCA) for disease control and plant growth promotion. In this study, 1308 Trichoderma strains were obtained from the plant rhizosphere soil, above-ground plants, and decaying wood from natural habitats in China. Among them, 49 Trichoderma strains showed a good inhibitory effect, especially against Botrytis cinerea, Fusarium oxysporum, and Colletotrichum gloeosporioides with inhibition rate above 85% in the dual culture test. Among these 49 strains, the 13 strains with broad-spectrum inhibitory effects also significantly promoted the seed germination of five crops (rice, cucumber, tomato, melon, and pakchoi) and root growth of four crop seedlings (watermelon, tomato, eggplant, and chili). Furthermore, these strains showed effective colonization in the rhizosphere and root of cucumber. Trichoderma strains SC012 and NX043 showed the highest chitinase and ß-1,3-glucanase activity among all strains. Based on the morphological characterization and phylogenetic analysis of the nuclear ribosomal internal transcribed spacer (ITS) and translation elongation factor 1 (tef1), twelve Trichoderma strains were identified as Trichoderma asperellum and one as Trichoderma afroharzianum. This study suggests that the 13 Trichoderma strains are promising BCAs and could be developed as biofertilizers and biological pesticides for agricultural applications.

Amide-bridged conjugated organic polymers: efficient metal-free catalysts for visible-light-driven CO2 reduction with H2O to CO.

The visible-light-driven photoreduction of CO2 to value-added chemicals over metal-free photocatalysts without sacrificial reagents is very interesting, but challenging. Herein, we present amide-bridged conjugated organic polymers (amide-COPs) prepared via self-condensation of amino nitriles in combination with hydrolysis, for the photoreduction of CO2 with H2O without any photosensitizers or sacrificial reagents under visible light irradiation. These catalysts can afford CO as the sole carbonaceous product without H2 generation. Especially, amide-DAMN derived from diaminomaleonitrile exhibited the highest activity for the photoreduction of CO2 to CO with a generation rate of 20.6 µmol g-1 h-1. Experiments and DFT calculations confirmed cyano/amide groups as active sites for CO2 reduction and second amine groups for H2O oxidation, and suggested that superior selectivity towards CO may be attributed to the adjacent redox sites. This work presents a new insight into designing photocatalysts for artificial photosynthesis.

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction.

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2 -promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400-700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2 )2 ] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g-1 , and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at -0.8 V and high current density (-141 mA cm-2 ) surpassing most of the metal-free electrocatalysts.

Hydrogen bonding-catalysed alcoholysis of propylene oxide at room temperature.

Alcoholysis of propylene oxide (PO) is achieved over azolate ionic liquids (IL, e.g., 1-hydroxyethyl-3-methyl imidazolium imidazolate) at room temperature, accessing glycol ethers in high yields with excellent selectivity (e.g., >99%). Mechanism investigation indicates that cooperation of hydrogen-bonding of the anion with methanol and that of the cation with PO catalyses the reaction.

Identification of microRNA-like RNAs from Trichoderma asperellum DQ-1 during its interaction with tomato roots using bioinformatic analysis and high-throughput sequencing.

MicroRNA-like small RNAs (milRNAs) and their regulatory roles in the interaction between plant and fungus have recently aroused keen interest of plant pathologists. Trichoderma spp., one of the widespread biocontrol fungi, can promote plant growth and induce plant disease resistance. To investigate milRNAs potentially involved in the interaction between Trichoderma and tomato roots, a small RNA (sRNA) library expressed during the interaction of T. asperellum DQ-1 and tomato roots was constructed and sequenced using the Illumina HiSeqTM 2500 sequencing platform. From 13,464,142 sRNA reads, we identified 21 milRNA candidates that were similar to other known microRNAs in the miRBase database and 22 novel milRNA candidates that possessed a stable microRNA precursor hairpin structure. Among them, three milRNA candidates showed different expression level in the interaction according to the result of stem-loop RT-PCR indicating that these milRNAs may play a distinct regulatory role in the interaction between Trichoderma and tomato roots. The potential transboundary milRNAs from T. asperellum and their target genes in tomato were predicted by bioinformatics analysis. The results revealed that several interesting proteins involved in plant growth and development, disease resistance, seed maturation, and osmotic stress signal transduction might be regulated by the transboundary milRNAs. To our knowledge, this is the first report of milRNAs taking part in the process of interaction of T. asperellum and tomato roots and associated with plant promotion and disease resistance. The results might be useful to unravel the mechanism of interaction between Trichoderma and tomato.

Hydrogen-bond donor and acceptor cooperative catalysis strategy for cyclic dehydration of diols to access O-heterocycles.

Dehydrative cyclization of diols to O-heterocycles is attractive, but acid and/or metal-based catalysts are generally required. Here, we present a hydrogen-bond donor and acceptor cooperative catalysis strategy for the synthesis of O-heterocycles from diols in ionic liquids [ILs; e.g., 1-hydroxyethyl-3-methyl imidazolium trifluoromethanesulfonate ([HO-EtMIm][OTf])] under metal-free, acid-free, and mild conditions. [HO-EtMIm][OTf] is tolerant to a wide diol scope, shows performance even better than H2SO4, and affords a series of O-heterocycles including tetrahydrofurans, tetrahydropyrans, morpholines, dioxanes, and thioxane in high yields. Mechanism investigation indicates that the IL cation and anion serve as hydrogen-bond donor and acceptor, respectively, to activate the C─O and O─H bonds of alcohol via hydrogen bonds, which synergistically catalyze dehydrative cyclization of diols to O-heterocycles. Notably, the products could be spontaneously separated after reaction because of their immiscibility with the IL, and the IL could be recycled. This green strategy has great potential for application in industry.

Photocatalytic Reduction of CO2 to CO over Quinacridone/BiVO4 Nanocomposites.

Solar energy-driven photoreduction of CO2 to energy-rich chemicals is of significance for sustainable development but challenging. Herein, quinacridone (QA)/nBiVO4 (n=0.2-20, in which n stands for the mass ratio of BiVO4 to QA) nanocomposites were developed for photoreduction of CO2 . Characterization of the materials with Fourier-transform (FT)IR spectroscopy and X-ray photoelectron spectroscopy (XPS) pointed to QA/nBiVO4 preparation via hydrogen-bonding-directed self-assembly of QA on BiVO4 nanosheets. Using triethanolamine (TEOA) as a sacrifice reagent, QA/10BiVO4 showed the best performance, affording CO with a production rate of 407 µmol g-1 h-1 , 24 times higher than those of pure QA. It was indicated that the Z-scheme charge-transfer mechanism of QA/nBiVO4 could significantly improve the separation and transmission efficiency of photo-generated electrons and holes. This novel approach provides new insight for fabricating the composite photocatalytic materials of small molecule organic semiconductors and inorganic semiconductors with high efficiency for photocatalytic of reduction CO2 .

Hydrogen-Bonding Catalyzed Ring-Closing C-O/C-O Metathesis of Aliphatic Ethers over Ionic Liquid under Metal-Free Conditions.

O-heterocycles have wide applications, and their efficient and green synthesis is very interesting. Herein, we report hydrogen-bonding catalyzed ring-closing metathesis of aliphatic ethers to O-heterocycles over ionic liquid (IL) catalyst under metal- and solvent-free conditions. The IL 1-butylsulfonate-3-methylimidazolium trifluoromethanesulfonate ([SO3 H-BMIm][OTf]) is discovered to show outstanding performance, better than the reported catalysts. An interface effect plays an important role in mediating the reaction rate due to the immiscibility between the products and the IL catalyst, and the products can be spontaneously separated. NMR analysis and DFT calculation suggest that a pair of cation and anion of [SO3 H-BMIm][OTf] could form three strong H-bonds with an ether molecule, which catalyze the ether transformation via a cyclic oxonium intermediate. A series of O-heterocycles including tetrahydrofurans, tetrahydropyrans, morpholines and dioxane can be obtained from their corresponding ethers in excellent yields (e.g., >99 %). This work opens an efficient and metal-free way to produce O-heterocycles from aliphatic ethers.