Niobium Modification of CeO2 Tuning Electron Density of Nickel-Ceria Interfacial Sites for Enhanced CO2 Methanation.

CO2 methanation has attracted considerable attention as a promising strategy for recycling CO2 and generating valuable methane. This study presents a niobium-doped CeO2-supported Ni catalyst (Ni/NbCe), which demonstrates remarkable performance in terms of CO2 conversion and CH4 selectivity, even when operating at a low temperature of 250 °C. Structural analysis reveals the incorporation of Nb species into the CeO2 lattice, resulting in the formation of a Nb-Ce-O solid solution. Compared with the Ni/CeO2 catalyst, this solid solution demonstrates an improved spatial distribution. To comprehend the impact of the Nb-Ce-O solid solution on refining the electronic properties of the Ni-Ce interfacial sites, facilitating H2 activation, and accelerating the hydrogenation of CO2* into HCOO*, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis and density functional theory (DFT) calculations were conducted. These investigations shed light on the mechanism through which the activity of CO2 methanation is enhanced, which differs from the commonly observed CO* pathway triggered by oxygen vacancies (OV). Consequently, this study provides a comprehensive understanding of the intricate interplay between the electronic properties of the catalyst's active sites and the reaction pathway in CO2 methanation over Ni-based catalysts.

Chemosensory proteins are associated with thiamethoxam tolerance in bird cherry-oat aphid Rhopalosiphum padi.

Rhopalosiphum padi (L.) is an important cosmopolitan pest of cereal crops. Thiamethoxam is widely used for control R. padi in some regions. Chemosensory proteins (CSPs) are a class of transporter proteins in arthropods which play a key role in various physiological processes including response to insecticide exposure. However, the role of R. padi CSPs (RpCSPs) in insecticide binding and susceptibility has not been well clarified. In this study, we found that the expression levels of RpCSP1, RpCSP4, RpCSP5, RpCSP7, RpCSP10 were dramatically upregulated after exposure to thiamethoxam. Suppression of RpCSP4 and RpCSP5 transcription by RNA interference significantly enhanced the susceptibility of R. padi to thiamethoxam. Molecular docking and fluorescence competitive binding showed that RpCSP4 and RpCSP5 had high binding affinity with thiamethoxam. The present results prove that RpCSP4 and RpCSP5 are related to insecticide resistance through high binding affinity to reduce the toxicity of insecticide.

Recombinant DTß4-inspired porous 3D vascular graft enhanced antithrombogenicity and recruited circulating CD93+/CD34+ cells for endothelialization.

Matching material degradation with host remodeling, including endothelialization and muscular remodeling, is important to vascular regeneration. We fabricated 3D PGS-PCL vascular grafts, which presented tunable polymer components, porosity, mechanical strength, and degrading rate. Furthermore, highly porous structures enabled 3D patterning of conjugated heparin-binding peptide, dimeric thymosin ß4 (DTß4), which played key roles in antiplatelets, fibrinogenesis inhibition, and recruiting circulating progenitor cells, thereafter contributed to high patency rate, and unprecedentedly acquired carotid arterial regeneration in rabbit model. Through single-cell RNA sequencing analysis and cell tracing studies, a subset of endothelial progenitor cells, myeloid-derived CD93+/CD34+ cells, was identified as the main contributor to final endothelium regeneration. To conclude, DTß4-inspired porous 3DVGs present adjustable physical properties, superior anticoagulating, and re-endothelializing potentials, which leads to the regeneration of small-caliber artery, thus offering a promising tool for vessel replacement in clinical applications.

The interaction of alkaloids in Coptis chinensis Franch -Tetradium ruticarpum (A. Juss.) T.G. Hartley with hOCT1 and hOCT2.

ETHNOPHARMACOLOGICAL RELEVANCE: Zuojin Pill, a traditional poly-herbal drug, comprises Coptis chinensis Franch - Tetradium ruticarpum (A. Juss.) T.G. Hartley (6:1). The significant quantity of alkaloids found in the participating herbs is a key aspect of the Zuojin Pill. According to traditional Chinese medicine (TCM), these numerous alkaloidal compounds within Zuojin Pill have various essential therapeutic effects. AIM OF THE STUDY: The alkaloids in Tetradium are mainly indole alkaloids, while the alkaloids in Coptis are mostly isoquinoline alkaloids with low bioavailability. Alkaloids and their metabolites are nitrogen-containing compounds or weakly alkaline substances that can be partially ionized under physiological pH conditions. Fortunately, organic cation transporters (OCTs) play a crucial role in the cellular uptake of weakly alkaline compounds. Therefore, we speculated that the alkaloidal compounds might interact with liver cation transporters hOCT1 and kidney cation transporters hOCT2 to alter cell drug disposal. In order to clarify our hypothesis, a series of alkaloids-OCTs interaction experiments were conducted. MATERIALS AND METHODS: HEK293 cells stably expressing hOCT1 and hOCT2 were modeled and evaluated. Afterward, high-content screening (HCS) was conducted to analyze whether the main alkaloids and their metabolites of Coptis - Tetradium were inhibitors of hOCT1 and hOCT2 transporters. Meanwhile, LC-MS/MS was used to investigate whether the alkaloidal compounds were substrates of hOCT1 and hOCT2 transporters. Finally, drug interactions at the cellular level were assessed by LC-MS/MS after co-administration of berberine and rutacorine. RESULTS: Berberine, jateorhizine, coptisine, epiberberine, columbamine, demethyleneberberine, and berberrubine could significantly inhibit hOCT1 and hOCT2 activity. Isoquinoline alkaloids, including berberine, jateorhizine, coptisine, epiberberine, columbamine, and palmatine, were substrates of hOCT1 and hOCT2, but not the indole alkaloids evodiamine and rutaecarpine. Furthermore, evodiamine at a concentration of 20 µmol/L had a trivial effect on berberine accumulation in HEK293-hOCT2 cells. CONCLUSIONS: These results support the idea that alkaloidal compounds within Coptis and Tetradium have hOCT1 and hOCT2 inhibitory activity or be their substrates, and the increased oral bioavailability of berberine in vivo was closely related to the potential interactions of small molecules in Coptis- Tetradium. Overall, our study provides a framework for investigating the potential interactions of small molecules in Coptis- Tetradium.

Boosting CO2 methanation on ceria supported transition metal catalysts via chelation coupled wetness impregnation.

The incipient wetness impregnation (IWI) method is widely used in the preparation of supported transition metal catalysts for its high throughput and cost-effective synthesis, yet suffers from poor metal-support interaction, restricting its further application at an industrial scale. Herein, a universal strategy of chelation coupled impregnation (CCI) is presented. The as-prepared Ni/CeO2(CCI) showed superior catalytic performance for CO2 conversion (84.3%) and CH4 selectivity (100%) under the experimental conditions (WGHSV = 24,000 mL g-1 h-1 and H2/CO2 = 4:1) even at low temperatures (T = 275 °C). The surface characterization results confirmed that the agglomeration of metal active sites in Ni/CeO2(CCI) was restricted and more surface oxygen vacancies were generated on CeO2. Further, the in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) analysis suggested that the surface oxygen vacancies that served as active sites could facilitate the direct dissociation of CO2 more favorably than the associative route, thus significantly promoting CO2 methanation activity.

Pharmacological manipulation of macrophage autophagy effectively rejuvenates the regenerative potential of biodegrading vascular graft in aging body.

Declined regenerative potential and aggravated inflammation upon aging create an inappropriate environment for arterial regeneration. Macrophages are one of vital effector cells in the immune microenvironment, especially during biomaterials mediated repairing process. Here, we revealed that the macrophage autophagy decreased with aging, which led to aggravated inflammation, thereby causing poor vascular remodeling of artificial grafts in aging body. Through loading the autophagy-targeted drugs, rapamycin and 3-MA (3-methyladenine), in PCL (polycaprolactone) sheath of the PGS (poly glycerol sebacate) - PCL vascular graft, the essential role of macrophage autophagy was confirmed in regulating macrophage polarization and biomaterial degradation. Moreover, the utilization of rapamycin promoted anti-inflammatory polarization of macrophage by activating autophagy, which further promoted myogenic differentiation of vascular progenitor cells and accelerated endothelialization. Our study elucidated the contribution of pharmacological manipulation of macrophage autophagy in promoting regeneration of small caliber artery, which may pave a new avenue for clinical translation of vascular grafts in aging body.

Mussel patterned with 4D biodegrading elastomer durably recruits regenerative macrophages to promote regeneration of craniofacial bone.

Crosstalk between bone marrow mesenchymal stem cells (BMSCs) and macrophages plays vital role in bone healing. By investigating the mechanism of collagen membrane-guided bone regeneration, we found compact structure and rapid membrane degradation compromised the duration of M2 macrophages influx, which restricts the recruitment of BMSCs that is essential for bone healing. To tackle this issue, a biodegrading elastomeric compound consisting of poly(glycerol sebacate) (PGS) and polycaprolactone (PCL) was fabricated into hierarchically porous membrane. The rational design of 3D microstructure enabled sufficient polydopamine (PDA) coating. Without any addition of growth factors, the 3D-patterned PDA membrane enables early and durable influx of M2 macrophages, which in turn promotes BMSCs recruitment and osteogenic differentiation. Furthermore, 4D-morphing of the membrane fully regenerates the dome shaped calvarial bone as well as arc-shape bone in peri-implant alveolar defect without filling xenogenous substitute. This study revealed the superiority of 3D printed microstructures in immunomodulatory materials. The availability of 4D-morphing for PGS/PCL construct expanded their advantages in reconstructing craniofacial bone.

Arming wood carbon with carbon-coated mesoporous nickel-silica nanolayer as monolithic composite catalyst for steam reforming of toluene.

Steam reforming is an effective measure for biomass tar elimination as well as H2-rich syngas (H2 + CO) production. However, the granular or powdery Ni-based catalysts are prone to deactivation, which is caused by inappropriate mass transfer and clogging of catalyst bed. Herein, monolithic wood carbon (WC) with low-tortuosity microchannels is armed with a carbon-coated mesoporous nickel-silica nanocomposite (Ni-SiO2@C) layer via an evaporation-induced self-assembly and calcination procedure for toluene (tar model compound) steam reforming. The quality of the Ni-SiO2@C layer growing on the surface of WC microchannel is affected by the molar ratios of Si/Ni feed. A uniform thin-layer coverage is obtained on the Ni-15SiO2@C/WC (Si/Ni = 15) catalyst, where highly dispersed Ni nanoparticles (average size of 6.6 nm) with appropriate metal-support interaction and remarkable mechanical strength are achieved. The mass transfer, coke resistance, and hydrothermal stability of the Ni-15SiO2@C/WC catalyst were significantly improved by the multilevel structure assembled from the WC microchannels and the secondary ordered SiO2 mesopores. A stable toluene conversion over 97% with an H2 yield of 135 µmol/min was obtained at 600 °C on the Ni-15SiO2@C/WC catalyst. This work opens a new window for facilely constructing high-performance wood carbon-based monolithic tar reforming catalyst.

Effect of Hot Rolling on the Microstructure and Properties of Nanostructured 15Cr ODS Alloys with Al and Zr Addition.

Oxide dispersion strengthened (ODS) alloys with Al and Zr addition have excellent radiation tolerance, high-temperature strength, and corrosion resistance. The 15Cr-Al-Zr-ODS alloys are processed by mechanical alloying (MA), hot isostatic pressing (HIP), subsequent hot rolling to large strains of 70%, and further annealing. The effect of hot rolling on the microstructure, and the properties of nanostructured 15Cr ODS alloys with Al and Zr addition, were investigated. The microstructure after hot rolling and annealing showed obvious anisotropy. The cubic texture (φ1 = 0°, Φ = 0°, φ2 = 0°) {0 0 1} <1 0 0> and brass-R texture (φ1 = 0°, Φ = 55°, φ2 = 45°) {1 1 1} <1 1 0> were observed. The similar size distribution of precipitates was obtained for the comparison of the hot rolling samples with the hot isostatic pressed samples, which can be attributed to excellent thermal stability. After hot rolling, the alloy showed higher yield strength but did not lose too much plasticity.

Dimeric Thymosin ß4 Loaded Nanofibrous Interface Enhanced Regeneration of Muscular Artery in Aging Body through Modulating Perivascular Adipose Stem Cell-Macrophage Interaction.

Regenerating nonthrombotic and compliant artery, especially in the aging body, remains a major surgical challenge, mainly owing to the inadequate knowledge of the major cell sources contributing to arterial regeneration and insufficient bioactivity of delivered peptides in grafts. Ultrathin nanofibrous sheaths stented with biodegrading elastomer present opening channels and reduced material residue, enabling fast cell recruitment and host remodeling, while incorporating peptides offering developmental cues are challenging. In this study, a recombinant human thymosin ß4 dimer (DTß4) that contains two complete Tß4 molecules is produced. The adult perivascular adipose is found as the dominant source of vascular progenitors which, when stimulated by the DTß4-loaded nanofibrous sheath, enables 100% patency rates, near-complete structural as well as adequate functional regeneration of artery, and effectively ameliorates aging-induced defective regeneration. As compared with Tß4, DTß4 exhibits durable regenerative activity including recruiting more progenitors for endothelial cells and smooth muscle cells, when incorporated into the ultrathin polycaprolactone sheath. Moreover, the DTß4-loaded interface promotes smooth muscle cells differentiation, mainly through promoting M2 macrophage polarization and chemokines. Incorporating artificial DTß4 into ultrathin sheaths of fast degrading vascular grafts creates an effective interface for sufficient muscular remodeling thus offering a robust tool for vessel replacement.

Microstructure and Low-Cycle Fatigue Behavior of Al-9Si-4Cu-0.4Mg-0.3Sc Alloy with Different Casting States.

The low-cycle fatigue behavior of Al-9Si-4Cu-0.4Mg-0.3Sc alloy with different casting states was investigated by performing low-cycle fatigue tests and by means of observations and analysis with a scanning electron microscope (SEM) and a transmission electron microscope (TEM). It was found that the metal-mold cast and die-cast Al-9Si-4Cu-0.4Mg-0.3Sc alloys exhibited the cyclic stress response of strain hardening under all imposed total strain amplitudes. The cyclic deformation resistance and fatigue life of the metal-mold cast Al-9Si-4Cu-0.4Mg-0.3Sc alloy were lower than those of the die-cast Al-9Si-4Cu-0.4Mg-0.3Sc alloy. The plastic strain and elastic strain amplitudes of the metal-mold cast and die-cast Al-9Si-4Cu-0.4Mg-0.3Sc alloys were linearly related to the number of reversals to failure, which obeyed the Coffin-Manson and Basquin formulas, respectively. The results of TEM observation revealed that at all imposed total strain amplitudes, the cyclic deformation mechanisms of the metal-mold cast and die-cast Al-9Si-4Cu-0.4Mg-0.3Sc alloys were planar slip and wavy slip at the lower and higher strain amplitudes, respectively.

Damage Adaptive Titanium Alloy by in-Situ Elastic Gradual Mechanism.

Natural materials are generally damage adaptive through their multilevel architectures, with the characteristics of compositional and mechanical gradients. This study demonstrated that the desired elastic gradient can be in-situ stress-induced in a titanium alloy, and that the alloy showed extreme fatigue-damage tolerance through the crack deflection and branch due to the formation of a three-dimensional elastically graded zone surrounding the crack tip. This looks like a perceptive and adaptive mechanism to retard the crack: the higher stress concentrated at the tip and the larger elastic gradient to be induced. The retardation is so strong that a gradient nano-grained layer with a thickness of less than 2 µm formed at the crack tip due to the highly localized and accumulated plasticity. Furthermore, the ultrafine-grained alloy with the nano-sized precipitation also exhibited good damage tolerance.

Fast degrading elastomer stented fascia remodels into tough and vascularized construct for tracheal regeneration.

Tracheal reconstruction remains a major surgical challenge, mainly owing to the scarce of resilient hollow grafts with identifiable vascular pedicle in humans. In this study, we developed a three-layer, elastomeric, trachea-like composite made of poly glycerol sebacate (PGS) and polycaprolactone (PCL), which presented appropriate resilient property, timely degradation and interconnected pores. C shape PCL rings fabricated with selective laser sintering (SLS) techniques are regularly positioned around porous PGS tubes and fixed by PCL electrospinning sheath. Such an elastomeric composite underwent host remodeling including rapid vascularization and tissue infiltration after fascia wrapping. With degrading of PGS, C rings well incorporated into growing fascia and lead to the formation of pedicled tracheal grafts, which attributes to the strong and resilient properties of generated hollow grafts thus enabled orthotopic transplantation in segmental tracheal defect. Progressive remodeling on such vascularized and mechanically stable grafts resulted in epithelium regeneration on luminal side as well as production of adequate amount of collagen and elastin, which warrantees the air passage during breathing. Future study employing large animal models more representative of human tracheal regeneration is warranted before clinical translation. Using fast degrading PGS combined with PCL rings represents a philosophical shift from the prevailing focus on tough grafts in airway reconstruction and may impact regenerative medicine in general.

Evolution of Secondary α Phase during Aging Treatment in Novel near ß Ti-6Mo-5V-3Al-2Fe Alloy.

Evolution of secondary α phase during aging treatment of a novel near ß titanium alloy Ti-6Mo-5V-3Al-2Fe(wt.%) was studied by OM, SEM, and TEM. Results indicated that size and distribution of secondary α phase were strongly affected by aging temperature and time. Athermal ω phase formed after super-transus solution treatment followed by water quenching, and promoted nucleation of needle-like intragranular α in subsequent aging process. When aged at 480 °C, fine scaled intragranular α with small inter-particle spacing precipitated within ß grains and high ultimate tensile strength above 1500 MPa was achieved. When the aging temperature increased, the size and inter-particle spacing of intragranular α increased and made the strength reduce, but the ductility got improved. When aging temperature reached as high as 600 °C, ω phase disappeared and intragranular α coarsened obviously, resulting in serious decrease of strength. While mutually parallel Widmanstätten α laths formed at the vicinity of ß grain boundaries and grew into the internal area of ß grains, and significant improvement of ductility was achieved. As the aging time increased from 4 h to 16 h at 600 °C, the intragranular α grew slightly and brought about minor change of mechanical properties.