BACKGROUND: Despite recent advances the prognosis of pulmonary hypertension remains poor and warrants novel therapeutic options. Extensive studies, including ours, have revealed that hypoxia-induced pulmonary hypertension is associated with high oxidative stress. Cerium oxide nanozyme or nanoparticles (CeNPs) have displayed catalytic activity mimicking both catalase and superoxide dismutase functions and have been widely used as an anti-oxidative stress approach. However, whether CeNPs can attenuate hypoxia-induced pulmonary vascular oxidative stress and pulmonary hypertension is unknown.
RESULTS: In this study, we designed a new ceria nanozyme or nanoparticle (AuCeNPs) exhibiting enhanced enzyme activity. The AuCeNPs significantly blunted the increase of reactive oxygen species and intracellular calcium concentration while limiting proliferation of pulmonary artery smooth muscle cells and pulmonary vasoconstriction in a model of hypoxia-induced pulmonary hypertension. In addition, the inhalation of nebulized AuCeNPs, but not CeNPs, not only prevented but also blunted hypoxia-induced pulmonary hypertension in rats. The benefits of AuCeNPs were associated with limited increase of intracellular calcium concentration as well as enhancement of extracellular calcium-sensing receptor (CaSR) activity and expression in rat pulmonary artery smooth muscle cells. Nebulised AuCeNPs showed a favorable safety profile, systemic arterial pressure, liver and kidney function, plasma Ca2+ level, and blood biochemical parameters were not affected.
CONCLUSIONS: We conclude that AuCeNPs is an improved reactive oxygen species scavenger that effectively prevents and treats hypoxia-induced pulmonary hypertension.

The damage threshold of an Au-coated flat mirror, one of the reflective optics installed on the FEL-2 beamline of the Dalian Coherent Light Source, China, upon far-UV free-electron laser irradiation is evaluated. The surface of the coating is characterized by profilometer and optical microscope. A theoretical approach of the phenomenon is also presented, by application of conventional single-pulse damage threshold calculations, a one-dimensional thermal diffusion model, as well as finite-element analysis with ANSYS.

Photocatalytic CO2 conversion is a prospective way to mitigate greenhouse effect. In2O3 is widely used in the resource conversion of CO2, but still exists a few drawbacks containing limited CO2 capture and activation, narrow light absorption range, low charge separation and utilization. To overcome these disadvantages, an NH2-UiO-66/Au/In2O3 composite photocatalyst is built, with Au nanoparticles and NH2-UiO-66 decorated on the surface of In2O3 nanorods. Significantly, the improved carrier separation ability is attributed to the Schottky junction at the Au/In2O3 interface and the heterostructure between In2O3 and NH2-UiO-66. And the widened light absorption is attributed to the plasmon effect caused by Au nanoparticles. Moreover, the increase of CO2 adsorption and activation is mainly due to the porosity of NH2-UiO-66, thereby greatly improving photocatalytic CO2RR efficiency of NH2-UiO-66/Au/In2O3 nanorods. The CO yield of NH2-UiO-66/Au/In2O3 is 8.56 μmol g-1 h-1, which is nearly 45 times that of In2O3. This work will present a novel idea to design high-efficient composite photocatalysts for CO2 reduction by multifunctional component synergistic enhancement.

Au decorated with type I collagen (Col) was used as a core material to cross-link with stromal cell-derived factor 1α (SDF1α) in order to investigate biological performance. The Au-based nanoparticles were subjected to physicochemical determination using scanning electron microscopy (SEM), dynamic light scattering (DLS) and ultraviolet-visible (UV-Vis) and Fourier-transform infrared spectroscopy (FTIR). Mesenchymal stem cells (MSCs) were used to evaluate the biocompatibility of this nanoparticle using the MTT assay and measuring reactive oxygen species (ROS) production. Also, the biological effects of the SDF-1α-conjugated nanoparticles (Au-Col-SDF1α) were assessed and the mechanisms were explored. Furthermore, we investigated the cell differentiation-inducing potential of these conjugated nanoparticles on MSCs toward endothelial cells, neurons, osteoblasts and adipocytes. We then ultimately explored the process of cell entry and transportation of the nanoparticles. Using a mouse animal model and retro-orbital sinus injection, we traced in vivo biodistribution to determine the biosafety of the Au-Col-SDF1α nanoparticles. In summary, our results indicate that Au-Col is a promising drug delivery system; it can be used to carry SDF1α to improve MSC therapeutic efficiency.

Direct and selective oxidation of benzene to phenol is a long-term goal in industry. Although great efforts have been made in homogenous catalysis, it still remains a huge challenge to drive this reaction via heterogeneous catalysts under mild conditions. Herein, a single-atom Au loaded MgAl-layered double hydroxide (Au1 -MgAl-LDH) with a well-defined structure, in which the Au single atoms are located on the top of Al3+ with Au-O4 coordination as revealed by extended x-ray-absorption fine-structure (EXAFS)and density-functional theory (DFT)calculation is reported. The photocatalytic results prove the Au1 -MgAl-LDH is capable of driving benzene oxidation reaction with O2 in water, and exhibits a high selectivity of 99% for phenol. While contrast experiment shows a ≈99% selectivity for aliphatic acid with Au nanoparticle loaded MgAl-LDH (Au-NP-MgAl-LDH). Detailed characterizations confirm that the origin of the selectivity difference can be attributed to the profound adsorption behavior of substrate benzene with Au single atoms and nanoparticles. For Au1 -MgAl-LDH, single Au-C bond is formed in benzene activation and result in the production of phenol. While for Au-NP-MgAl-LDH, multiple AuC bonds are generated in benzene activation, leading to the crack of CC bond.

Aerogels derived from the colloidal nanoparticles featured with hierarchical interconnected pore-rich networks guarantee their great potentials in various applications. Herein, the controllable assembly of three-dimensional aerogels based on Au nanoparticles (Au NPs) and reduced graphene oxide (rGO) nanosheets as building blocks via a bottom-up approach have been systematically clarified. The difference of building blocks and their assembly sequence were crucially to the final aerogel morphologies and electrochemical properties. Specifically, the highly porous graphene-gold dual aerogels (rGO-Au DAGs) with interconnected rGO nanosheets and Au nanowires showed high conductivity, large surface area and good biocompatibility. Thus, it was employed as an excellent matrix to immobilize enzyme for high-efficient bioelectrocatalysis. Taking bilirubin oxidase as an example, a more positive on-set potential (0.60 V) and a larger catalytic current density (0.77 mA cm-2@0.40 V) than those of other rGO-Au assemblies were achieved for direct bioelectrocatalytic O2 reduction. This study will provide an efficient strategy for unique dual-structural aerogels design and shed light to develop new functional materials for bioelectrocatalytic applications such as biosensors and biofuel cells.

The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH3) has been recognized as an effective, carbon-neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N2 adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO2 nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO2-x) as the electrocatalyst for efficient N2-fixing. The experimental results demonstrate that OVs act as active sites, which enable efficient chemisorption and activation of N2 molecules. The Au nanoparticles loaded on the OVs-rich TiO2 nanosheets not only accelerate charge transfer but also change the local electronic structure, thus enhancing N2 adsorption and activation. In this work, the optimal Au/TiO2-x electrocatalyst displays a considerable NH3 yield activity of 12.5 μg h-1 mgcat.-1 and a faradaic efficiency (FE) of 10.2 % at -0.40 V vs reversible hydrogen electrode (RHE). More importantly, the Au/TiO2-x exhibits a stable N2-fixing activity in cycling and it persists even after 80 h of consecutive electrolysis. Density functional theory (DFT) calculations reveal that the OVs serve as the active sites in TiO2, while Au nanoparticles are crucial for improving N2 chemisorption and lowering the reaction energy barrier by facilitating the charge transfer for eNRR with a distal hydrogenation pathway. This research offers a rational catalytic site design for modulating charge transfer of active sites on metal-supported defective catalysts to boost N2 electroreduction to NH3.

As an emerging technology, nanocatalytic medicine attracts much attention, especially the ones according to the enzymatic reaction by using excess H2O2 in the tumor. Among various candidates, single-atom catalyst (SAC) revealed unique and outstanding redox reaction performance, since the active sites consisting of single metal atoms may achieve the maximum utilization of metal atoms and emerge obviously amplified reaction rate. Here we developed an M-Nx (M = Mn, Zn) center-based SAC with a hollow structure by calcination of Mn2+-doped zeolitic imidazolate frameworks (ZIF-8), and PEGylation was applied to improve the hydrophilicity. According to the enzymatic reaction, the M-Nx (M = Mn, Zn) centers have an inherent peroxidase-like activity to catalyze over-expressed H2O2 in the weak acidic tumor microenvironment and generate a large amount of toxic reactive oxygen species (ROS) like hydroxyl radicals for therapy. To keep efficient therapeutic output, we integrated the hollow SAC with Au which could expend the glucose in tumor and supply H2O2 as the substrate of peroxidase-like activity. Better yet, Au may boost the photothermal effect of SAC and offer another non-invasive photothermal therapy (PTT) to promote the effect of tumor removal. This platform provided a new idea for the construction of more efficient peroxidase-like activity in tumor therapy.

Similar to the metal centers in biocatalysis and homogeneous catalysis, the metal species in single atom catalysts (SACs) are charged, atomically dispersed and stabilized by support and substrate. The reaction condition dependent catalytic performance of SACs has long been realized, but seldom investigated before. We investigated CO oxidation pathways over SACs in reaction conditions using atomically dispersed Au on h-BN (AuBN) as a model with extensive first-principles-based calculations. We demonstrated that the adsorption of reactants, namely CO, O2 and CO2, and their coadsorption with reaction species on AuBN would be condition dependent, leading to various reaction species with different reactivity and impact the CO conversion. Specifically, the revised Langmuir-Hinshelwood pathway with the CO-mediated activation of O2 and dissociation of cyclic peroxide intermediate followed by the Eley-Rideal type reduction is dominant at high temperatures, while the coadsorbed CO-mediated dissociation of peroxide intermediate becomes plausible at low temperatures and high CO partial pressures. Carbonate species would also form in existence of CO2, react with coadsorbed CO and benefit the conversion. The findings highlight the origin of the condition-dependent CO oxidation performance of SACs in detailed conditions and may help to rationalize the current understanding of the superior catalytic performance of SACs.

The photocatalytic reduction of carbon dioxide (CO2) to fossil fuels has attracted widespread attention. However, obtaining the high value-added hydrocarbons, especially C2+ products, remains a considerable challenge. Herein, gold (Au) nanoparticle-modified bismuth-rich bismuth oxybromide Bi12O17Br2 nanotube composites were designed and tested. Au nanoparticles act as electron traps and thermal electron donors that promote the efficient separation and migration of carriers to form the C2+ product. As a result, compared with the pure Bi12O17Br2 nanotubes, Au@Bi12O17Br2 composites can not only produce the carbon monoxide (CO) and methane (CH4), but also covert CO2 into ethane (C2H6). In this study, Au@Bi12O17Br2-700 was used to obtain a C2H6 production rate of 29.26 μmol h-1 g-1. The selectivities during a 5-hour test reached 94.86% for hydrocarbons and 90.81% for C2H6. The proposed approach could be used to design high-performance photocatalysts to convert CO2 into high value-added hydrocarbon products.