Promoting Molecular Exchange on Rare-Earth Oxycarbonate Surfaces to Catalyze the Water-Gas Shift Reaction.

It is highly desirable to fabricate an accessible catalyst surface that can efficiently activate reactants and desorb products to promote the local surface reaction equilibrium in heterogeneous catalysis. Herein, rare-earth oxycarbonates (Ln2O2CO3, where Ln = La and Sm), which have molecular-exchangeable (H2O and CO2) surface structures according to the ordered layered arrangement of Ln2O22+ and CO32- ions, are unearthed. On this basis, a series of Ln2O2CO3-supported Cu catalysts are prepared through the deposition precipitation method, which provides excellent catalytic activity and stability for the water-gas shift (WGS) reaction. Density functional theory calculations combined with systematic experimental characterizations verify that H2O spontaneously dissociates on the surface of Ln2O2CO3 to form hydroxyl by eliminating the carbonate through the release of CO2. This interchange efficiently promotes the WGS reaction equilibrium shift on the local surface and prevents the carbonate accumulation from hindering the active sites. The discovery of the unique layered structure provides a so-called "self-cleaning" active surface for the WGS reaction and opens new perspectives about the application of rare-earth oxycarbonate nanomaterials in C1 chemistry.

Bamboo polysaccharides elicit hypocrellin A biosynthesis of a bambusicolous fungus Shiraia sp. S9.

Hypocrellin A (HA), a fungal perylenequinone from bambusicolous Shiraia species, is a newly developed photosensitizer for photodynamic therapy in cancer and other infectious diseases. The lower yield of HA is an important bottleneck for its biomedical application. This study is the first report of the enhancement of HA production in mycelium culture of Shiraia sp. S9 by the polysaccharides from its host bamboo which serve as a strong elicitor. A purified bamboo polysaccharide (BPSE) with an average molecular weight of 34.2 kDa was found to be the most effective elicitor to enhance fungal HA production and characterized as a polysaccharide fraction mainly composed of arabinose and galactose (53.7: 36.9). When BPSE was added to the culture at 10 mg/L on day 3, the highest HA production of 422.8 mg/L was achieved on day 8, which was about 4.0-fold of the control. BPSE changed the gene expressions mainly responsible for central carbon metabolism and the cellular oxidative stress. The induced generation of H2O2 and nitric oxide was found to be involved in both the permeabilization of cell membrane and HA biosynthesis, leading to enhancements in both intra- and extracellular HA production. Our results indicated the roles of plant polysaccharides in host-fungal interactions and provided a new elicitation technique to improve fungal perylenequinone production in mycelium cultures.

The signaling role of extracellular ATP in co-culture of Shiraia sp. S9 and Pseudomonas fulva SB1 for enhancing hypocrellin A production.

BACKGROUND: Adenosine 5'-triphosphate (ATP) plays both a central role as an intracellular energy source, and a crucial extracellular signaling role in diverse physiological processes of animals and plants. However, there are less reports concerning the signaling role of microbial extracellular ATP (eATP). Hypocrellins are effective anticancer photodynamic therapy (PDT) agents from bambusicolous Shiraia fungi. The co-culture of Shiraia sp. S9 and a bacterium Pseudomonas fulva SB1 isolated from Shiraia fruiting bodies was established for enhanced hypocrellin A (HA) production. The signaling roles of eATP to mediate hypocrellin biosynthesis were investigated in the co-culture. RESULTS: The co-culture induced release of eATP at 378 nM to the medium around 4 h. The eATP release was interdependent on cytosolic Ca2+ concentration and reactive oxygen species (ROS) production, respectively. The eATP production could be suppressed by the Ca2+ chelator EGTA or abolished by the channel blocker La3+, ROS scavenger vitamin C and NADPH oxidase inhibitor diphenyleneiodonium chloride (DPI). The bacterium-induced H2O2 production was strongly inhibited by reactive blue (RB), a specific inhibitor of membrane purinoceptors, but dependent on the induced Ca2+ influx in the co-culture. On the other hand, the application of exogenous ATP (exATP) at 10-300 µM to Shiraia cultures also promoted fungal conidiation and HA production, both of which were blocked effectively by the purinoceptor inhibitors pyridoxalphosphate-6-azophenyl-2', 4'-disulfonic acid (PPADS) and RB, and ATP hydrolase apyrase. Both the induced expression of HA biosynthetic genes and HA accumulation were inhibited significantly under the blocking of the eATP or Ca2+ signaling, and the scavenge of ROS in the co-culture. CONCLUSIONS: Our results indicate that eATP release is an early event during the intimate bacterial-fungal interaction and eATP plays a signaling role in the bacterial elicitation on fungal metabolites. Ca2+ and ROS are closely linked for activation of the induced ATP release and its signal transduction. This is the first report on eATP production in the fungal-bacterial co-culture and its involvement in the induced biosynthesis of fungal metabolites.

Chitosan aerosol inhalation alleviates lipopolysaccharide- induced pulmonary fibrosis in rats.

PURPOSE: Pulmonary fibrosis (PF) is an insidiously progressive scarring disorder of the alveoli and is associated with high mortality. Currently, therapies available are associated with restricted efficacy and side effects. This study aimed to investigate the effect of chitosan aerosol inhalation on lipopolysaccharide (LPS)-induced pulmonary remodeling and fibrosis in rats. METHODS: A rat model of PF was established by intratracheal injection of LPS (5 mg/kg). Chitosan was nebulized to rats from day 4 to 28 after LPS injection. We analyzed the effect of chitosan on LPS-induced pulmonary remodeling and fibrosis by hematoxylin-eosin staining (HE), Masson staining, and the determination of the hydroxyproline content. The expression intensities of matrix metalloproteinase-3 (MMP-3) and tissue inhibitor of metalloproteinase-1 (TIMP-1) were analyzed by western blots. RESULTS: Histological assessments showed that chitosan aerosol inhalation attenuated the fibrotic changes in LPS-induced PF in rats. Compared with the LPS group, the fibrosis parameters were significantly improved in the LPS + chitosan group (LCh group), although not as good as those of the control group. The expressions of MMP-3 and TIMP-1 in the LCh group were markedly less than that of the LPS group on the 28th day. CONCLUSIONS: Our findings show that chitosan aerosol inhalation inhibits the expression of MMP-3 and TIMP-1, and ameliorates LPS-induced pulmonary remodeling and fibrosis in rats.

Protective effect of arctiin against Toxoplasma gondii HSP70-induced allergic acute liver injury by disrupting the TLR4-mediated activation of cytosolic phospholipase A2 and platelet-activating factor.

Toxoplasma gondii (T. gondii)-derived heat shock protein 70 (T.g.HSP70) is a toxic protein that downregulates host defense responses against T. gondii infection. T.g.HSP70 was proven to induce fatal anaphylaxis in T. gondii infected mice through cytosolic phospholipase A2 (cPLA2) activated-platelet-activating factor (PAF) production via Toll-like receptor 4 (TLR4)-mediated signaling. In this study, we investigated the effect of arctiin (ARC; a major lignan compound of Fructus arctii) on allergic liver injury using T.g.HSP70-stimulated murine liver cell line (NCTC 1469) and a mouse model of T. gondii infection. Localized surface plasmon resonance, ELISA, western blotting, co-immunoprecipitation, and immunofluorescence were used to investigate the underlying mechanisms of action of ARC on T. gondii-induced allergic acute liver injury. The results showed that ARC suppressed the T.g.HSP70-induced allergic liver injury in a dose-dependent manner. ARC could directly bind to T.g.HSP70 or TLR4, interfering with the interaction between these two factors, and inhibiting activation of the TLR4/mitogen-activated protein kinase/nuclear factor-kappa B signaling, thereby inhibiting the overproduction of cPLA2, PAF, and interferon-γ. This result suggested that ARC ameliorates T.g.HSP70-induced allergic acute liver injury by disrupting the TLR4-mediated activation of inflammatory mediators, providing a theoretical basis for ARC therapy to improve T.g.HSP70-induced allergic liver injury.

Catalytic properties of trivalent rare-earth oxides with intrinsic surface oxygen vacancy.

Oxygen vacancy (Ov) is an anionic defect widely existed in metal oxide lattice, as exemplified by CeO2, TiO2, and ZnO. As Ov can modify the band structure of solid, it improves the physicochemical properties such as the semiconducting performance and catalytic behaviours. We report here a new type of Ov as an intrinsic part of a perfect crystalline surface. Such non-defect Ov stems from the irregular hexagonal sawtooth-shaped structure in the (111) plane of trivalent rare earth oxides (RE2O3). The materials with such intrinsic Ov structure exhibit excellent performance in ammonia decomposition reaction with surface Ru active sites. Extremely high H2 formation rate has been achieved at ~1 wt% of Ru loading over Sm2O3, Y2O3 and Gd2O3 surface, which is 1.5-20 times higher than reported values in the literature. The discovery of intrinsic Ov suggests great potentials of applying RE oxides in heterogeneous catalysis and surface chemistry.

Can digital economy improve employment structure?-Mediating effect based on a spatial Durbin model.

Based on the panel data of 283 prefecture-level cities in China from 2011 to 2019, this study constructed an index measurement system of digital economy, economic agglomeration, innovation and entrepreneurship, and employment structure. The index of digital economy was developed by entropy weight method, and the double-fixed spatial Durbin model was constructed based on the intermediary effect from the spatial perspective to determine the direct effect, indirect effect, and total effect of the digital economy, economic agglomeration degree, and innovation and entrepreneurship on employment structure. The results indicated a significant spatial correlation between the three aspects, i.e., digital economy can significantly optimize the employment structure, with an evident spillover effect. The mechanism analysis revealed that the level of innovation and entrepreneurship poses a stronger intermediary effect than the degree of economic agglomeration, and the digital economy in the eastern region directly impacts the urban employment structure; however, the influence of digital economy on the employment structure is significantly higher in small- and medium-sized cities than in large-sized cities.

Combination of Biochar and Functional Bacteria Drives the Ecological Improvement of Saline-Alkali Soil.

The addition of functional bacteria (FB) is low-cost and is widely applied in saline-alkali soil remediation, which may gradually become ineffective due to inter-specific competition with indigenous bacteria. To improve the adaptability of FB, the target FB strains were isolated from local saline-alkali soil, and the combined effects of FB and biochar were explored. The results showed that FB isolated from local soil showed better growth than the purchased strains under high saline-alkali conditions. However, the indigenous community still weakened the function of added FB. Biochar addition provided a specific niche and increased the relative abundance of FB, especially for Proteobacteria and Bacteroidota. As a result, the co-addition of 10% biochar and FB significantly increased the soil available phosphorus (AP) by 74.85% and available nitrogen (AN) by 114.53%. Zea Mays's growth (in terms of height) was enhanced by 87.92% due to the decreased salinity stress and extra nutrients provided.

GALNT3 protects against vascular calcification by reducing oxidative stress and apoptosis of smooth muscle cells.

Vascular calcification (VC) is the pathological deposition of calcium and phosphate minerals in blood vessels, which is a common complication of atherosclerosis. Polypeptide N-acetylgalactosamine transferase 3 (GALNT3) initiates O-glycosylation of proteins through addition of GalNAc to specific serine or threonine residues. Our previous studies revealed the potent role of GALNT3 in atherosclerosis, whereas the precise mechanisms remain obscure. This study investigated the regulatory effect and mechanism of GALNT3 on VC. Firstly, GALNT3 was overexpressed and knocked down by adenovirus in high-phosphate induced calcified HASMCs and overexpressed by adeno-associated virus in vitamin D3-induced arterial calcification mice. We showed that the calcium deposition and mRNA expression of osteogenic markers MSX2, ALPL, and Runx2 were all significantly reduced with GALNT3 overexpression. Moreover, overexpression of GALNT3 significantly down-regulated the expression of the oxidative stress markers Nox2 and Nox4, up-regulated total antioxidant capacity, decreased the expression of pro-inflammatory factors IL-1ß, TNF-α and IL-8, matrix metalloproteinases MMP2 and MMP9, as well as reduced the apoptosis of cells in phosphate induced HASMCs. Furthermore, Vicia Villosa Lectin (VVL) pull down and TNFR1 immunoprecipitation assays showed that GALNT3 overexpression increased O-GalNAcylation of TNFR1 and blocked the activation of NF-κB signaling pathway. In addition, GALNT3 attenuates vitamin D3-induced aortic calcification in mice by alleviating oxidative stress and apoptosis of smooth muscle cells. In conclusion, this study indicates that GALNT3 protects against VC by reducing oxidative stress, vascular inflammation, and apoptosis of smooth muscle cells through the TNFR1/NF-κB signaling pathway. Thus, GALNT3 may be a potential therapeutic target for VC.

Structure characterization of an exopolysaccharide from a Shiraia-associated bacterium and its strong eliciting activity on the fungal hypocrellin production.

Hypocrellins are fungal perylenequinones (PQs) from Shiraia fruiting bodies and potential photosensitizers for cancer photodynamic therapy. Shiraia fruiting bodies harbor diverse bacterial communities dominated by Pseudomonas. The present study was to characterize the exopolysaccharide (EPS) of P. fulva SB1 which acted as an elicitor to stimulate the PQ accumulation of the host Shiraia. A bacterial EPS named EPS-1 was purified from the culture broth of P. fulva SB1, which consisted of mannose (Man) and glucose (Glc) with an average molecular weight of 9.213 × 104 Da. EPS-1 had (1 â†’ 2)-linked α-mannopyranose (Manp) backbone and side chains of α-D-Manp-(1→ and α-D-Manp-(1 â†’ 6)-ß-D-Glcp-(1 â†’ 6)-α-D-Manp(1 â†’ group attached to the O-6 positions of (1 â†’ 2)-α-D-Manp. EPS-1 at 30 mg/L stimulated both intracellular and extracellular hypocrellin A (HA) by about 3-fold of the control group. The EPS-1 treatment up-regulated the expression of key genes for HA biosynthesis. The elicitation of HA biosynthesis by EPS-1 was strongly dependent on the induced reactive oxygen species (ROS) generation. The results may provide new insights on the role of bacterial EPS in bacterium-fungus interactions and effective elicitation strategy for hypocrellin production in mycelial cultures.

Boron regulates catalytic sites of biochar to enhance the formation of surface-confined complex for improved peroxydisulfate activation.

Biochar has been developed to activate persulfate for wastewater treatment due to its carbon essence, easily-available and low-cost. Efficiently active sites and interfacial electron transfer are highly desired for peroxydisulfate (PDS) activation. In this study, boronic ester structure and defect degree of boron-doped biochar are confirmed as activate sites to improve PDS activation. The performance of pollutants degradation is proven to have structure-activity relationships with both activate sites. Moreover, boron-doped biochar exhibits higher stability and oxidation potential by forming the surface-confined complex, promoting electron transfer from pollutants to complex. The optimized boron-doped biochar has the advantages of adapting to a broad pH range (2.9-10.0), strong resistance to Cl- and organic matters, a low activation energy of 11.22 kJ mol-1, and achieving the decomposition of practical dyeing wastewater. Our work provides a promising approach to regulating the interfacial catalytic sites of biochar by doping heteroatom for PDS activation in practical wastewater treatment.

Insights into the highly efficient treatment of dyeing wastewater using algal bloom derived activated carbon with wide-range adaptability to solution pH and temperature.

Here, a low-cost acid-base and temperature tolerant algal bloom derived activated carbon (ABAC) was successfully prepared to remove rhodamine B (RhB) from water. The ABAC exhibited maximum adsorption capacity of RhB (1101 ± 11 mg/g), higher than that of laboratory-prepared rape straw activated carbon (176 ± 5 mg/g) and commercial activated carbon (489 ± 5 mg/g). It is attributed to larger surface area and mesoporous structure of the ABAC. Furthermore, the effective adsorption of RhB by using ABAC was achieved at a wide range of solution pH (3.2-10.8) and temperature(25-50 °C). The mass transfer resistance of RhB adsorption process well depicted by Langmuir model was controlled by external mass transfer. The adsorption process involved both secondly chemisorption (H-bonds and π-π interaction) and dominated physisorption. Four dyes in river water were efficiently removed. This work provides a promising approach for developing high-absorption biomass materials for actual dye wastewater treatment.

An integrated biological-electrocatalytic process for highly-efficient treatment of coking wastewater.

Coking wastewater is typically refractory, mainly due to its biological toxicity and complex composition. In this study, a novel integrated biological-electrocatalytic process consisting of two three-dimensional electrochemical reactors (3DERs), two biological aerated filters (BAFs), and a three-dimensional biofilm electrode reactor (3DBER) is developed for the advanced treatment of coking wastewater. 73.21% of chemical oxygen demand (COD), 38.02% of ammonium nitrogen (NH4+-N) and 91.46% of nitrate nitrogen (NO3--N) are removed by 3DERs. BAFs mainly convert NH4+-N to NO3--N through microbial nitrification. The 3DBER removes the residual NO3--N by bio-electrochemical denitrification. The integrated system can eliminate 74.72-83.27% of COD, 99.38-99.74% of NH4+-N, and 69.64-99.83% of total nitrogen from coking wastewater during the continuous operation, as well as significantly reducing the toxicity of the wastewater. The superiorities of the integrated 3DERs/BAFs/3DBER system recommend the application of such biological-electrocatalytic technology in the treatment of highly toxic wastewater.

Unique structure of active platinum-bismuth site for oxidation of carbon monoxide.

As the technology development, the future advanced combustion engines must be designed to perform at a low temperature. Thus, it is a great challenge to synthesize high active and stable catalysts to resolve exhaust below 100 °C. Here, we report that bismuth as a dopant is added to form platinum-bismuth cluster on silica for CO oxidation. The highly reducible oxygen species provided by surface metal-oxide (M-O) interface could be activated by CO at low temperature (~50 °C) with a high CO2 production rate of 487 µmolCO2·gPt-1·s-1 at 110 °C. Experiment data combined with density functional calculation (DFT) results demonstrate that Pt cluster with surface Pt-O-Bi structure is the active site for CO oxidation via providing moderate CO adsorption and activating CO molecules with electron transformation between platinum atom and carbon monoxide. These findings provide a unique and general approach towards design of potential excellent performance catalysts for redox reaction.

Electricity production enhancement in a constructed wetland-microbial fuel cell system for treating saline wastewater.

The use of constructed wetlands in combination with microbial fuel cells (CW-MFC) to treat saline wastewater may enhance electricity production by increasing the ionic strength, reducing internal resistance and stimulating microbes to accelerate electron transfer. In this study, salinity did not significantly inhibit the removal of TP and COD, but TN and NH4+-N removal efficiencies during saline wastewater treatment (ST) were significantly lower than during non-saline wastewater treatment (NT). However, salinity significantly increased the power density (16.4 mW m-2 in ST and 3.9 mW m-2 in NT, a 4-fold enhancement) by increasing the electron transfer rate and reducing internal resistance (140.29â€¯Ω in ST and 415.21â€¯Ω in NT). The peptides in extracellular polymeric substances (EPS) acted as electron shuttles to promote the migration of electrons and protons in ST. From start-up to stable operation, though the microorganisms in ST were reduced in diversity relative to NT, the proportion of electrochemically active bacteria (EAB), such as Ochrobactrum, significantly increased (p < 0.05) and gradually predominated in the microbial community.

Risk factor analysis of 167 patients with high myopia.

AIM: To analyze the risk factors of age, sex, course, best corrected visual acuity (BCVA), diopter and fundus features of high myopes with progressive high myopia. METHODS: A total of 167 patients with high myopes were categorized into four groups: group 1, age 10-29 years; group 2, age 30-49 years; group 3, age 50-69 years and group 4, age 70-89 years. The refractive errors of all patients were measured without cycloplegia with an autorefractometer. Data of the spherical equivalent (SE) of the refractive errors in diopters (D) and fundus examined by direct ophthalmoscope were used in statistical analysis. RESULTS: The number of female was statistically larger than that of male (P<0.01), also the disease course was correlated to the age. The visual acuity of high myopes significantly decreased as they grew older including the higher incidence of lacquer cracker, submacular hemorrhage, Fuchs spots, chorioretinal atrophy. CONCLUSION: Female maybe a risk factor of high myopia, advanced age is an important factor of visual acuity decreased. High myopes ought to be treated early to delay the progress of myopia and development of macular degeneration.