Dual Channel H2O2 Photosynthesis in Pure Water over S-Scheme Heterojunction Cs3PMo12/CC Boosted by Proton and Electron Reservoirs.

Dual channel photo-driven H2O2 production in pure water on small-scale on-site setups is a promising strategy to provide low-concentrated H2O2 whenever needed. This process suffers, however, strongly from the fast recombination of photo-generated charge carriers and the sluggish oxidation process. Here, insoluble Keggin-type cesium phosphomolybdate Cs3PMo12O40 (abbreviated to Cs3PMo12) is introduced to carbonized cellulose (CC) to construct S-scheme heterojunction Cs3PMo12/CC. Dual channel H2O2 photosynthesis from both H2O oxidation and O2 reduction in pure water has been thus achieved with the production rate of 20.1 mmol L-1 gcat. -1 h-1, apparent quantum yield (AQY) of 2.1% and solar-to-chemical conversion (SCC) efficiency of 0.050%. H2O2 accumulative concentration reaches 4.9 mmol L-1. This high photocatalytic activity is guaranteed by unique features of Cs3PMo12/CC, namely, S-scheme heterojunction, electron reservoir, and proton reservoir. The former two enhance the separation of photo-generated charge carriers, while the latter speeds up the torpid oxidation process. In situ experiments reveal that H2O2 is formed via successive single-electron transfer in both channels. In real practice, exposing the reaction system under natural sunlight outdoors successfully results in 0.24 mmol L-1 H2O2. This work provides a key practical strategy for designing photocatalysts in modulating redox half-reactions in photosynthesis.

Untargeted Metabolomics Reveals Alterations of Rhythmic Pulmonary Metabolism in IPF.

Idiopathic pulmonary fibrosis (IPF) is a chronic and progressive condition characterized by the impairment of alveolar epithelial cells. Despite continued research efforts, the effective therapeutic medication is still absent due to an incomplete understanding of the underlying etiology. It has been shown that rhythmic alterations are of significant importance in the pathophysiology of IPF. However, a comprehensive understanding of how metabolite level changes with circadian rhythms in individuals with IPF is lacking. Here, we constructed an extensive metabolite database by utilizing an unbiased reference system culturing with 13C or 15N labeled nutrients. Using LC-MS analysis via ESI and APCI ion sources, 1300 potential water-soluble metabolites were characterized and applied to evaluate the metabolic changes with rhythm in the lung from both wild-type mice and mice with IPF. The metabolites, such as glycerophospholipids and amino acids, in WT mice exhibited notable rhythmic oscillations. The concentrations of phospholipids reached the highest during the fast state, while those of amino acids reached their peak during fed state. Similar diurnal variations in the metabolite rhythm of amino acids and phospholipids were also observed in IPF mice. Although the rhythmic oscillation of metabolites in the urea cycle remained unchanged, there was a significant up-regulation in their levels in the lungs of IPF mice. 15N-ammonia in vivo isotope tracing further showed an increase in urea cycle activity in the lungs of mice with IPF, which may compensate for the reduced efficiency of the hepatic urea cycle. In sum, our metabolomics database and method provide evidence of the periodic changes in lung metabolites, thereby offering valuable insights to advance our understanding of metabolic reprogramming in the context of IPF.

Dynamic Expression of Palmitoylation Regulators across Human Organ Development and Cancers Based on Bioinformatics.

Protein palmitoylation is a reversible modification process that links palmitate to cysteine residues via a reversible thioester bond. Palmitoylation exerts an important role in human organ development and tumor progression. However, a comprehensive landscape regarding the dynamic expression of palmitoylation regulators in human organ development remains unclear. In this study, we analyzed the dynamic expression of palmitoylation regulators in seven organ development and eight cancer types based on bioinformatics. We found that the expression levels of most palmitoylation regulators were altered after birth. In particular, ZDHHC7/20/21 exhibited converse expression patterns in multiple cancer types. Survival analysis showed that the poor prognosis in patients with kidney renal clear carcinoma (KIRC) is related to low expression of ZDHHC7/20/21, and a high expression of ZDHHC7/20/21 is related to worse survival in patients with liver hepatocellular carcinoma (LIHC). Furthermore, we found that the expression of ZDHHC7 is associated with infiltration levels of some types of immune cells in the tumor microenvironment (TME), and we explored the relationship between ZDHHC7 expression and immune checkpoint (ICP) genes across 33 cancer types. In addition, gene set enrichment analysis (GSEA) results indicated that ZDHHC7 might regulate different genes to mediate the same pathway in different organs. In summary, the comprehensive analysis of palmitoylation regulators reveals their functions in human organ development and cancer, which may provide new insights for developing new tumor markers.

Cordycepin enhances hyperthermia-induced apoptosis and cell cycle arrest by modulating the MAPK pathway in human lymphoma U937 cells.

BACKGROUND: Hyperthermia induces cancer cell death. However, the cytotoxic effect of hyperthermia is not sufficient. Cordycepin can also induce apoptosis in cancer cells and enhance the antitumoral activity of irradiation. To examine cordycepin-mediated enhancement of hyperthermia-induced apoptosis, this study investigated the combined effects and apoptotic mechanisms of hyperthermia and cordycepin on human leukemia U937 cells. METHODS: Cell viability and apoptosis were measured using MTT assays, Hoechst 33342 staining and Annexin V/PI double staining. The distribution of the cell cycle and sub-G1 phase, reactive oxygen species (ROS) and mitochondrial membrane potential (MMP) were examined by flow cytometry. The expression of related proteins was analyzed by western blotting. RESULTS: Combined treatment with hyperthermia and cordycepin markedly augmented apoptosis by upregulating Bax and suppressing Bcl-2, Bid and activated caspase 3 and 8 expression, and apoptosis was decreased by Z-VAD-fmk (a pan caspase inhibitor). We also found that the MMP was significantly decreased and excessive ROS generation occurred. The combination treatment also induced arrest in the G2/M phase by downregulating cyclin dependent kinase 1 (CDK1) and cyclin B1 protein expression. Furthermore, it was observed that mitogen-activated protein kinase (MAPK) pathway including ERK, JNK and p38 signals was involved in the induction of apoptosis. The phosphorylated p38 and JNK were increased and ERK phosphorylation was decreased by the combined treatment. In addition, N-acetyl-L-cysteine (NAC) significantly protected the cells by restoring ROS levels and the activity of caspase-3, inactivating the MAPK pathway. CONCLUSION: Cordycepin significantly enhanced hyperthermia-induced apoptosis and G2/M phase arrest in U937 cells. The combined treatment enhanced apoptosis through the MAPK pathway and mitochondrial dysfunction, and these effects could be rescued by NAC. We report for the first time that cordycepin can be used as a hyperthermia sensitizer to treat leukemia.

Solvent-Free Synthesized Monolithic Ultraporous Aluminas for Highly Efficient Removal of Remazol Brilliant Blue R: Equilibrium, Kinetic, and Thermodynamic Studies.

In this study, ultraporous aluminas (UPA) were synthesized as new effective adsorbents for Remazol Brilliant Blue R (RBBR) removal from aqueous solutions. The UPA monoliths were grown via facile oxidation process, followed by isochronous annealing treatment in air at different temperatures, through which γ, θ, and α phase polycrystalline fibrous grains of UPA can be accordingly obtained. The experimental factors that affect the material adsorption performances including initial pH, contact time, and temperature were comprehensively studied by batch experiments. The RBBR adsorption isotherms of UPA(γ) and UPA(θ) powders were found almost identical, while UPA(α) powders showed low effectiveness. To obtain the desirable mechanical stability of the UPA monolith with considerable RBBR adsorption capacity, UPA(θ) powders were further studied. The UPA(θ) powders exhibited maximum RBBR adsorption at pH 2 due to the positively charged surface under acidic conditions. Compared with the Lagergren pseudo-first-order model, the pseudo-second-order model was found to explain the adsorption kinetics better. Despite the film diffusion dominating the adsorption process, the contributions of the intraparticle diffusion and chemical reactions were also found significant. The adsorption equilibrium data at different temperatures were fitted by the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) isotherm models. The Langmuir model was found the most effective in the description of equilibrium data, and the maximum RBBR adsorption capacity retained by UPA(θ) powders was 122.55 mg·g-1 at 295 K. Thermodynamic parameters (ΔG0, ΔH0, and ΔS0) indicated the adsorption process was spontaneous and exothermic in nature.

Discharge Regimes Transition and Characteristics Evolution of Nanosecond Pulsed Dielectric Barrier Discharge.

Discharge regime transition in a single pulse can present the breakdown mechanism of nanosecond pulsed dielectric barrier discharge. In this paper, regime transitions between streamer, diffuse, and surface discharges in nanosecond pulsed dielectric barrier discharge are studied experimentally using high resolution temporal-spatial spectra and instantaneous exposure images. After the triggering time of 2-10 ns, discharge was initiated with a stable initial streamer channel propagation. Then, transition of streamer-diffuse modes could be presented at the time of 10-34 ns, and a surface discharge can be formed sequentially on the dielectric plate. In order to analyze the possible reason for the varying discharge regimes in a single discharge pulse, the temporal-spatial distribution of vibrational population of molecular nitrogen N2 (C3Πu, v = 0,1,2) and reduced electric field were calculated by the temporal-spatial emission spectra. It is found that at the initial time, a distorted high reduced electric field was formed near the needle electrode, which excited the initial streamer. With the initial streamer propagating to the dielectric plate, the electric field was rebuilt, which drives the transition from streamer to diffuse, and also the propagation of surface discharge.

Sorbent track: Quantitative monitoring of adsorbed VOCs under in-situ plasma exposure.

Sorbent-TRACK is a new device developed to monitor adsorption and surface oxidation of pollutants under direct plasma exposure. It is based on direct transmitted Fourier Transformed Infrared (FTIR) spectroscopy. A pyrex reactor under controlled gas pressure and composition is inserted on the infrared beam of a commercially available Nicolet 5700 FTIR spectrometer. A substrate holder is located on the optical path of the infrared beam. A thin pellet of a dedicated catalyst (CeO2 in the present work) is inserted in a substrate holder and can be exposed to direct plasma treatment using a Dielectric Barrier Discharge. The time resolution of Sorbent-TRACK is limited by the time resolution of the Nicolet 5700 FTIR spectrometer and close to 30 s. The dynamic of the adsorption and plasma oxidation of acetone and isopropanol on CeO2 are studied and intermediates are monitored. Performances and sensitivity of Sorbent-TRACK are reported Adsorption and oxidation of acetone leads to production of adsorbed isobutene and acetic acid, where oxidation of isopropanol gives mainly to adsorbed acetone, mesityl oxide and acetate. An increase of the plasma power leads to an increase of the isopropanol and acetone oxidation rate and a related increase of the production of adsorbed intermediates.

Nucleation and growth kinetics of zirconium-oxo-alkoxy nanoparticles.

Nucleation and growth of zirconium-oxo-alkoxy (ZOA) nanoparticles were studied in a sol-gel process in n-propanol solution at a hydrolysis ratio H between 1.0 and 2.7 and zirconium-n-propoxyde precursor concentrations between 0.10 and 0.15 mol l(-1). The chemical transformations were conducted in quasi-perfect micromixing conditions (Damköhler number Da ≤ 1) and the nanoparticle size evolution was monitored in situ with the light scattering method. The size of primary nanoparticles (nuclei) 2R0 = 3.6 nm was found to be almost independent of the preparation conditions. A remarkable similarity with the titanium-oxo-alkoxy (TOA) nanoparticles was observed. In particular, both systems show the induction stage of the sol-gel growth for a hydrolysis ratio H > 2.0 and stable oxometallate units for H≤ 2.0. However in contrast to TOA, no stable hierarchical ZOA units (clusters) with R0≥R≥ 1.0 nm were observed, which makes this system less stable against aggregation, leading to polydispersed nanoparticles.