Polyoxometalate Confined Synthesis of BiVO Nanocluster for Urea Production with Remarkable O/N Tolerance.

Urea electrosynthesis from flue gas and NO under operating conditions represents a promising alternative technology to traditional energy-intensive industrial process. Herein, we explore a polyoxometalate confined synthesis strategy to prepare ultrafine BiVO nanocluster by pre-incorporating [VO] into NH-MIL-101-Al (MIL) framework. The resulting BiVO@MIL-n can efficiently drive co-reduction of NO and CO to urea.

Loading Dyes into Chiral Cd/Zn-Metal-Organic Frameworks for Efficient Full-Color Circularly Polarized Luminescence.

Host-guest chemistry of chiral metal-organic frameworks (MOFs) has endowed them with circularly polarized luminescence (CPL), it is still limited for MOFs to systematically tune full-color CPL emissions and sizes. This work directionally assembles the chiral ligands, metal sites and organic dyes to prepare a series of crystalline enantiomeric D/L-Cd/Zn-n MOFs (n=1~5, representing the adding amount of dyes), where D/L-Cd/Zn with the formula of Cd(D/L-Cam)(TPyPE) and Zn(D/L-Cam)(TPyPE) (D/L-Cam=D/L-camphoric acid, TPyPE=4,4',4'',4'''-(1,2-henediidenetetra-4,1-phenylene)tetrakis[pyridine]) were used as the chiral platforms. The framework-dye-enabled emission and through-space chirality transfer facilitate D/L-Cd/Zn-n bright full-color CPL activity.

Polyoxometalate-Based Single-Atom Catalyst with Precise Structure and Extremely Exposed Active Site for Efficient H Evolution.

Single-atom catalysts with precise structure and extremely high catalytic efficiency remain a fervent focus in the fields of materials chemistry and catalytic science. Herein, a nickel-substituted polyoxometalate (POM) {NiSbO(HO)[β-Ni(hmta)SbWO]} (NiPOM) with one extremely exposed nickel site [NiO(HO)] was synthesized using the conventional aqueous method. The uniform dispersion of single nickel center with well-defined structure was facilely achieved by anchoring nanosized NiPOM on graphene oxide (GO).

Single Dispersion of Fe(HO)-Based Polyoxometalate on Polymeric Carbon Nitride for Biomimetic CH Photooxidation.

Direct methane conversion to value-added oxygenates under mild conditions with in-depth mechanism investigation has attracted wide interest. Inspired by methane monooxygenase, the KNaFe(HO){[γ-SiWOFe(HO)]}·25HO polyoxometalate (Fe-POM) with well-defined Fe(HO) sites is synthesized to clarify the key role of Fe species and their microenvironment toward CH photooxidation. The Fe-POM can efficiently drive the conversion of CH to HCOOH with a yield of 1570.

Earth-abundant Zn-dipyrrin chromophores for efficient CO photoreduction.

The development of strong sensitizing and Earth-abundant antenna molecules is highly desirable for CO reduction through artificial photosynthesis. Herein, a library of Zn-dipyrrin complexes (-) are rationally designed via precisely controlling their molecular configuration to optimize strong sensitizing Earth-abundant photosensitizers. Upon visible-light excitation, their special geometry enables intramolecular charge transfer to induce a charge-transfer state, which was first demonstrated to accept electrons from electron donors.

Single-cluster Functionalized TiO Nanotube Array for Boosting Water Oxidation and CO Photoreduction to CHOH.

Solar-driven CO reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CHOH and CHCHOH dominated by multi-electron transfer. Single-cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge.

Building Co-N-Based UiO-MOF to Expand Design Parameters for MOF Photosensitization.

The construction of secondary building units (SBUs) in versatile metal-organic frameworks (MOFs) represents a promising method for developing multi-functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high-nuclear transition-metal-based UiO-architecture Co-MOF-BDC with visible-light-absorbing capacity. Remarkably, the N molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible-light-absorbing chromophores via click reaction.

Identification of Crucial Photosensitizing Factors to Promote CO -to-CO Conversion.

The sensitizing ability of a catalytic system is closely related to the visible-light absorption ability, excited-state lifetime, redox potential, and electron-transfer rate of photosensitizers (PSs), however it remains a great challenge to concurrently mediate these factors to boost CO photoreduction. Herein, a series of Ir(III)-based PSs (Ir-1-Ir-6) were prepared as molecular platforms to understand the interplay of these factors and identify the primary factors for efficient CO photoreduction. Among them, less efficient visible-light absorption capacity results in lower CO yields of Ir-1, Ir-2 or Ir-4.

Intravenous immunoglobulin for treatment of hospitalized COVID-19 patients: an evidence mapping and meta-analysis.

Background: The clinical efficacy and safety of intravenous immunoglobulin (IVIg) treatment for COVID-19 remain controversial. This study aimed to map the current status and gaps of available evidence, and conduct a meta-analysis to further investigate the benefit of IVIg in COVID-19 patients.

Methods: Electronic databases were searched for systematic reviews/meta-analyses (SR/MAs), primary studies with control groups, reporting on the use of IVIg in patients with COVID-19.

Water-Mediated Selectivity Control of CH OH versus CO/CH in CO Photoreduction on Single-Atom Implanted Nanotube Arrays.

Controllable methanol production in artificial photosynthesis is highly desirable due to its high energy density and ease of storage. Herein, single atom Fe is implanted into TiO /SrTiO (TSr) nanotube arrays by two-step anodization and Sr-induced crystallization. The resulting Fe-TSr with both single Fe reduction centers and dominant oxidation facets (001) contributes to efficient CO photoreduction and water oxidation for controlled production of CH OH and CO/CH .

Ordered Integration and Heterogenization of Catalysts and Photosensitizers in Metal-/Covalent-Organic Frameworks for Boosting CO Photoreduction.

ConspectusSolar-driven CO reduction into value-added chemicals, such as CO, HCOOH, CH, and C products, has been regarded as a potential way to alleviate environmental pollution and the energy crisis. In the past decades, numerous pioneered homogeneous catalytic systems composed of soluble photosensitizers (PSs) and catalytic active sites (CASs) have been explored for CO photoreduction. Nevertheless, inefficient electron migration based on random collision between CASs and PSs in homogeneous catalytic systems usually causes mediocre performance.

CO Cycloaddition under Ambient Conditions over Cu-Fe Bimetallic Metal-Organic Frameworks.

Carbon dioxide cycloaddition into fine chemicals is prospective technology to solve energy crisis and environmental issues. However, high temperature and pressure are usually required in the conventional cycloaddition reactions of CO with epoxides. Moreover, metal active sites play a vital role in the CO cycloaddition, but it is still unclear.

Truncated SCRIB isoform promotes breast cancer metastasis through HNRNP A1 mediated exon 16 skipping.

Breast cancer is one of the most common malignant tumors with high mortality due to metastases. SCRIB, a scaffold protein mainly distributed in the cell membrane, is a potential tumor suppressor. Mislocalization and aberrant expression of SCRIB stimulate the EMT pathway and promote tumor cell metastasis.

Photoacoustic imaging-guided triple-responsive nanoparticles with tumor hypoxia relief for improving chemotherapy/ photothermal/photodynamic synergistic therapy against breast cancer.

Chemo-photothermal/photodynamic synergistic therapy is a new effective cancer treatment method to overcome the limitations of single chemotherapy. However, the limited low photothermal conversion efficiency, the hypoxic tumor microenvironment, and premature leakage of the drug constrain their clinical applications. To address these challenges, an all-in-one biodegradable polydopamine-coated UiO-66 framework nanomedicine (DUPM) was developed to co-deliver the drug doxorubicin hydrochloride (DOX) and the excellent photothermal material MoO nanoparticles (NPs).

Construction of a non-negative matrix factorization model of immunogenic cell death-related genes in lung adenocarcinoma and analysis of survival prognosis.

Purpose: To explore the effectiveness of the model based on non-negative matrix factorization (NMF), analyze the tumor microenvironment and immune microenvironment for evaluating the prognosis of lung adenocarcinoma, establish a risk model, and screen independent prognostic factors.

Methods: Downloading the transcription data files and clinical information files of lung adenocarcinoma from TCGA database and GO database, the R software was used to establish the NMF cluster model, and then the survival analysis between groups, tumor microenvironment analysis, and immune microenvironment analysis was performed according to the NMF cluster result. R software was used to construct prognostic models and calculate risk scores.

Adjuvant-Free COVID-19 Vaccine with Glycoprotein Antigen Oxidized by Periodate Rapidly Elicits Potent Immune Responses.

Modification of antigens to improve their immunogenicity represents a promising direction for the development of protein vaccine. Here, we designed facilely prepared adjuvant-free vaccines in which the N-glycan of SARS-CoV-2 receptor-binding domain (RBD) glycoprotein was oxidized by sodium periodate. This strategy only minimally modifies the glycans and does not interfere with the epitope peptides.

Graphene Oxide-Mediated Synthesis of Ultrathin Co-MOL for CO Photoreduction.

Metal-organic framework (MOF) materials have broad application prospects in catalysis because of their ordered structure and molecular adjustability. However, the large volume of bulky MOF usually leads to insufficient exposure of the active sites and the obstruction of charge/mass transfer, which greatly limits their catalytic performance. Herein, we developed a simple graphene oxide (GO) template method to fabricate ultrathin Co-metal-organic layer (2.

Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO Photoreduction.

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center.

[Coupling Relationship Between Soil Functions and Environmental Factors Along an Altitudinal Gradient: A Case Study of the Meili Mountain].

Soil respiration and extracellular enzyme activity are important components of the material cycle of mountain ecosystems and play key roles in maintaining ecosystem functions. To explore the coupling relationship between soil functions and environmental factors, the soil functional indicators, environmental factors, and effects of altitude on the soil function of 36 soil samples from 12 altitudes of the Meili Mountain were analyzed. The results showed that there were significant differences in soil respirations and enzyme activities among altitudes of Meili Mountain, and high-altitude areas had higher soil functions.

pH-Sensitive and Biodegradable Mn(PO)·3HO Nanoparticles as an Adjuvant of Protein-Based Bivalent COVID-19 Vaccine to Induce Potent and Broad-Spectrum Immunity.

Developing a novel and potent adjuvant with great biocompatibility for immune response augmentation is of great significance to enhance vaccine efficacy. In this work, we prepared a long-term stable, pH-sensitive, and biodegradable Mn(PO)·3HO nanoparticle (nano-MnP) by simply mixing MnCl/NaHPO/NaHPO solution for the first time and employed it as an immune stimulant in the bivalent COVID-19 protein vaccine comprised of wild-type S1 (S1-WT) and Omicron S1 (S1-Omicron) proteins as antigens to elicit a broad-spectrum immunity. The biological experiments indicated that the nano-MnP could effectively activate antigen-presenting cells through the cGAS-STING pathway.

Novel sialoglycan linkage for constructing adjuvant-protein conjugate as potent vaccine for COVID-19.

Self-adjuvanting protein vaccines have been proved to be highly immunogenic with efficient codelivery of adjuvant and antigen. Current protein vaccines with built-in adjuvants are all modified at the peptide backbone of antigen protein, which could not achieve minor epitope interference and adjuvant multivalency at the same time. Herein, we developed a new conjugate strategy to construct effective adjuvant-protein vaccine with adjuvant cluster effect and minimal epitope interference.

Self-Adjuvanting Protein Vaccine Conjugated with a Novel Synthetic TLR4 Agonist on Virus-Like Liposome Induces Potent Immunity against SARS-CoV-2.

Exploring potent adjuvants and new vaccine strategies is crucial for the development of protein vaccines. In this work, we synthesized a new TLR4 agonist, structurally simplified lipid A analogue GAP112, as a potent built-in adjuvant to improve the immunogenicity of SARS-CoV-2 spike RBD protein. The new TLR4 agonist GAP112 was site-selectively conjugated on the N-terminus of RBD to construct an adjuvant-protein conjugate vaccine in a liposomal formulation.