Publications by authors named "Zirui Gao"

The use of reactive supports to disperse metal species is crucial for constructing highly efficient interfacial catalysts, by tuning the competitive reactant adsorption-activation pattern in supported metal catalysts into a non-competitive mechanism. However, these reactive supports are prone to deterioration during catalysis, limiting the lifespan of the catalyst and their potential practical applications. New strategies are needed to simultaneously protect reactive supports and surface metal species without compromising the inherent catalytic performance.

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Single-shot ptychography is a quantitative phase imaging method wherein overlapping beams of light arranged in a grid pattern simultaneously illuminate a sample, allowing a full ptychographic dataset to be collected in a single shot. It is primarily used at optical wavelengths, but there is interest in using it for x-ray imaging. However, constraints imposed by x-ray optics have limited the resolution achievable to date.

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Metal carbides with earth-abundant elements are widely regarded as promising alternatives to noble metal catalysts. Although comparable catalytic performances have been observed for metal carbides in several types of reactions, precise control of reaction pathways on them remains a formidable challenge, partially due to strong adsorption of reactants or intermediates. In this study, we show that bimolecular dehydrogenation of methanol to methyl formate and H is kinetically favored on bare α-MoC catalysts, while monomolecular dehydrogenation to CO and H becomes the dominant pathway when α-MoC is decorated with crowding atomic Ni species.

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Tumor immunotherapy has emerged as a formidable strategy, demonstrating substantial achievements in the field of cancer treatment. Despite its remarkable success, intrinsic limitations such as insufficient targeting capabilities, side effects, and resistance to immunotherapy hinder its efficacy. To address these challenges, the utilization of nanomedicines in tumor immunotherapy has been broadly explored, capitalizing on their advantages of targeting delivery capability, loading capacity, modifiability, and biocompatibility.

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The functionality of materials is determined by their composition and microstructure, that is, the distribution and orientation of crystalline grains, grain boundaries and the defects within them. Until now, characterization techniques that map the distribution of grains, their orientation and the presence of defects have been limited to surface investigations, to spatial resolutions of a few hundred nanometres or to systems of thickness around 100 nm, thus requiring destructive sample preparation for measurements and preventing the study of system-representative volumes or the investigation of materials under operational conditions. Here we present X-ray linear dichroic orientation tomography (XL-DOT), a quantitative, non-invasive technique that allows for an intragranular and intergranular characterization of extended polycrystalline and non-crystalline materials in three dimensions.

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Article Synopsis
  • Metal and acid sites are vital in heterogeneous catalysis and their interplay can significantly enhance catalytic performance.
  • This study introduces a method to combine these sites on a nanodiamond@graphene support, demonstrating how their arrangement affects the conversion of cyclohexanol into various products.
  • The catalyst featuring both acid and Pd sites achieves over 80% selectivity for benzene, highlighting the potential of integrated catalyst design for improved efficiency in industrial applications.
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Prokaryotic anti-phage immune systems use TIR and cGAS-like enzymes to produce 1''-3'-glycocyclic ADP-ribose (1''-3'-gcADPR) and cyclic dinucleotide (CDN) and cyclic trinucleotide (CTN) signalling molecules, respectively, which limit phage replication. However, how phages neutralize these distinct and common systems is largely unclear. Here we show that the Thoeris anti-defence proteins Tad1 and Tad2 both achieve anti-cyclic-oligonucleotide-based anti-phage signalling system (anti-CBASS) activity by simultaneously sequestering CBASS cyclic oligonucleotides.

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  • Tomographic imaging of time-evolving samples is important but challenging, especially at the nanoscale due to limits in speed and resolution in current methods.
  • A new dynamic nanotomography technique was developed that enhances imaging efficiency using sparse dynamic imaging and 4D tomography modeling.
  • This technique significantly improves temporal resolution by 40 times and allows for detailed observations of the hydration process in polymer electrolyte fuel cell catalysts, aiding in the understanding and optimization of their performance.
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Electrocatalytic oxidation of C-H bonds in hydrocarbons represents an efficient and sustainable strategy for the synthesis of value-added chemicals. Herein, a highly selective and continuous-flow electrochemical oxidation process of toluene to various oxygenated products (benzyl alcohol, benzaldehyde, and benzyl acetate) is developed with the electrocatalytic membrane electrodes (ECMEs). The selectivity of target products can be manipulated via surface and interface engineering of CoO-based electrocatalysts.

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  • The Wnt/β-catenin signaling pathway is essential for important biological functions like development and cell growth, and its regulation is critical for normal physiological processes.
  • When this pathway is improperly activated due to mutations or other factors, it can lead to cancer development and progression.
  • Ongoing research is focused on creating therapies that target this pathway, with many new drugs being developed to improve cancer treatment outcomes by addressing the challenges associated with their use in therapy.
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  • Prokaryotic organisms use immune systems involving TIR and cGAS enzymes to produce signaling molecules that help combat phage infections.
  • Researchers discovered that the Thoeris anti-defense proteins Tad1 and Tad2 can neutralize this immune response by sequestering cyclic oligonucleotides produced by the immune system.
  • Tad1 and Tad2 operate independently but effectively inhibit these anti-phage systems by binding to various cyclic nucleotides and glycocyclic ADPR molecules, showcasing their capabilities as dual-function inhibitors against bacterial defenses.
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  • Myelinated axons transmit signals in the brain through action potentials, but accurately mapping their crossing paths is challenging due to influence from unrelated brain structures.
  • Small-angle X-ray scattering (SAXS) can specifically detect myelinated axons by identifying distinct peaks in their scattering patterns, allowing for better resolution of fiber crossings.
  • The study demonstrates SAXS's effectiveness in various brain samples and positions it as a reliable tool for validating fiber orientations obtained from other imaging techniques like diffusion MRI and microscopy.
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  • - Prurigo nodularis (PN) is a tough-to-treat skin condition that causes severe itching and discomfort, prompting the need for effective treatments with fewer side effects.
  • - A study involving 24 adults treated with dupilumab showed significant improvements in pruritus (itchiness) and quality of life after 16 weeks, with many patients experiencing substantial symptom relief.
  • - The treatment was found to be safe, with only a small percentage (16.6%) of patients reporting adverse effects, suggesting that dupilumab could be a promising option for managing PN.
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The development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge, especially for bioinspired syntheses that can access non-natural reactions. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighbored single-cobalt site/pyridinic-N site (Co-N/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds including silanols, borasiloxanes, and silyl ethers via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated.

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Healing large bone defects remains challenging in orthopedic surgery and is often associated with poor outcomes and complications. A major issue with bioengineered constructs is achieving a continuous interface between host bone and graft to enhance biological processes and mechanical stability. In this study, we have developed a new bioengineering strategy to produce oriented biocompatible 3D PLGA/aCaP nanocomposites with enhanced osseointegration.

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In cancer microenvironment, aberrant glycosylation events of ECM proteins and cell surface receptors occur. We developed a protocol to generate 3D bioprinted models of colorectal cancer (CRC) crosslinking hyaluronic acid and gelatin functionalized with three signalling glycans characterized in CRC, 3'-Sialylgalactose, 6'-Sialylgalactose and 2'-Fucosylgalactose. The crosslinking, performed exploiting azide functionalized gelatin and hyaluronic acid and 4arm-PEG-dibenzocyclooctyne, resulted in biocompatible hydrogels that were 3D bioprinted with commercial CRC cells HT-29 and patient derived CRC tumoroids.

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Article Synopsis
  • - Reforming methanol is a promising method for producing hydrogen on-board, addressing challenges in hydrogen storage and transportation, with key catalysts being metal/metal oxide and metal/carbide systems.
  • - The study developed a detailed reaction model to explain how methanol interacts with water over Pt/NiAlO, identifying crucial steps like the breaking of C-H and O-H bonds driven by surface intermediates.
  • - Findings highlight the essential role of surface intermediates in catalytic activity and introduce the concept of bidirectional spillover, suggesting new directions for designing effective catalytic systems.
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Hydrogen is increasingly being discussed as clean energy for the goal of net-zero carbon emissions, applied in the proton-exchange-membrane fuel cells (PEMFC). The preferential oxidation of CO (PROX) in hydrogen is a promising solution for hydrogen purification to avoid catalysts from being poisoned by the trace amount of CO in hydrogen-rich fuel gas. Here, we report the fabrication of a novel bimetallic Pt-Fe catalyst with ultralow metal loading, in which fully-exposed Pt clusters bonded with neighbor atomically dispersed Fe atoms on the defective graphene surface.

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  • Acetonitrile can be effectively coupled into succinonitrile, a key molecule for nylon production, using a light-driven dehydrogenative method that also generates green hydrogen energy.
  • The reaction, utilizing anatase TiO photocatalysts in water, achieves a high formation rate and selectivity for succinonitrile while maintaining mild reaction conditions.
  • Water acts as a cocatalyst, working with the photocatalysts to facilitate reactions that lead to succinonitrile production without toxic reagents and minimizing unwanted byproducts.
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Rhupus syndrome, as an overlap syndrome of rheumatoid arthritis (RA) and systemic lupus erythematosus (SLE), is relatively rare because of their substantially different immunopathological mechanisms. Herein, we report the first case of primary cutaneous anaplastic large cell lymphoma (PC-ALCL) in a patient with rhupus syndrome and Sjogren's syndrome and review the relevant literature. A 52-year-old Chinese woman with a history of rhupus syndrome and Sjogren's syndrome was treated with methotrexate, who developed gradually increasing nodules on the waist.

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  • A new catalytic system has been developed that efficiently captures carbon monoxide (CO) and converts it into valuable chemicals through N-formylation.
  • Using isolated iridium atoms supported on nanadiamond/graphene, the system produces N-formylmorpholine with impressive efficiency, achieving a turnover number of 5,120,000 and over 99% selectivity in a single batch reaction.
  • The process allows for CO captured in morpholine solution to be converted into N-formylmorpholine at a 51% conversion rate, demonstrating a successful integration of CO capture and chemical conversion.
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The structural heterogeneity of surface metal species, which is represented by the distribution in size, morphology, and local coordination environment of the active metal component, is almost inevitable in practical supported metal catalysts. This is often regarded as a major hindrance to the full utilization of metal loading and the high mass-specific catalytic activity. In this work, by quantitative evaluation of the individual reaction steps of a probe reaction, cyclohexanol dehydrogenation (an important reaction for hydrogen storage and transportation as well as high valued chemical production), we demonstrate that the inherent heterogeneity of supported Rhodium catalysts prepared by conventional synthesis has unique advantages in a complex heterogeneous catalytic reaction.

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Synthesis of atomically dispersed catalysts with high metal loading and thermal stability is challenging but particularly valuable for industrial application in heterogeneous catalysis. Here, we report a facile synthesis of a thermally stable atomically dispersed Ir/α-MoC catalyst with metal loading as high as 4 wt%, an unusually high value for carbide supported metal catalysts. The strong interaction between Ir and the α-MoC substrate enables high dispersion of Ir on the α-MoC surface, and modulates the electronic structure of the supported Ir species.

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Reversing the thermal induced sintering phenomenon and forming high temperature stable fine dispersed metallic centers with unique structural and electronic properties is one of the ever-lasting targets of heterogeneous catalysis. Here we report that the dispersion of metallic Ni particles into under-coordinated two-dimensional Ni clusters over γ-MoN is a thermodynamically favorable process based on the AIMD simulation. A Ni-4nm/γ-MoN model catalyst is synthesized and used to further study the reverse sintering effect by the combination of multiple in-situ characterization methods, including in-situ quick XANES and EXAFS, ambient pressure XPS and environmental SE/STEM etc.

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Trivalent arsenic (As) is an effective agent for treating patients with acute promyelocytic leukaemia, but its ionic nature leads to several major limitations like low effective concentrations in leukaemia cells and substantial off-target cytotoxicity, which limits its general application to other types of leukaemia. Here, building from our clinical discovery that cancerous cells from patients with different leukaemia forms featured stable and strong expression of CD71, we designed a ferritin-based As nanomedicine, As@Fn, that bound to leukaemia cells with very high affinity, and efficiently delivered cytotoxic As into a large diversity of leukaemia cell lines and patient cells. Moreover, As@Fn exerted strong anti-leukaemia effects in diverse cell-line-derived xenograft models, as well as in a patient-derived xenograft model, in which it consistently outperformed the gold standard, showing its potential as a precision treatment for a variety of leukaemias.

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