Adsorption-coupled Fenton type reduction of bromate in water by high-yield polymer-derived ceramic-supported nano-zerovalent iron.

Nano-zerovalent iron (nZVI) is a promising material for the removal of both organic and inorganic pollutants from contaminated water. This study investigates the potential of a novel composite of nZVI on a polymer-derived supporting ceramic (nZVI-PDC) synthesized via the liquid-phase reduction method for the simultaneous adsorption and Fenton-type reduction of bromate anion (BrO3-) in water. The nZVI nanoparticles were effectively anchored onto the PDC by impregnating high-yield carbon in a ferrous sulfate solution. The PDC facilitated the uniform dispersion of nZVI nanoparticles due to its multiple active sites distributed within mesocarbon cavities. The developed nZVI-PDC composite exhibited a high specific surface area of 837 m2 g-1 and an ordered mesoporous structure with a pore volume of 0.37 cm3 g-1. As an adsorbent, the nZVI-PDC composite exhibited a maximum adsorption capacity (qe) of 842 mg g-1 and a partition coefficient (KH) of 10.2 mg g-1 µM-1, as calculated by the pseudo-second-order model. As a catalyst, the composite demonstrated a reaction kinetic rate of 43.5 µmol g-1 h-1 within 6 h at pH 4, using a dosage of 60 mg L-1 nZVI-PDC and a concentration of 0.8 mmol L-1 H2O2. Comparatively, PDC exhibited a qe of 408 mg g-1, KH of 1.67 mg g-1 µM-1, and a reaction rate of 20.8 µmol g-1 h-1, while nZVI showed a qe of 456 mg g-1, KH of 2.30 mg g-1 µM-1, and a reaction rate of 27.2 µmol g-1 h-1. The modelling indicated that the nZVI-PDC composite followed pseudo-second-order kinetics. The remarkable removal efficiency of the nZVI-PDC composite was attributed to the synergistic effects between PDC and nZVI, where PDC facilitated charge transfer, promoting Fe2+ generation and the Fe3+/Fe2+ cycle. Overall, this work introduces a promising adsorption technology for the efficient removal of BrO3- from contaminated aqueous solutions, highlighting the significant potential of the nZVI-PDC composite in water purification applications.

Green and highly effective extraction of bioactive flavonoids from Fructus aurantii employing deep eutectic solvents-based ultrasonic-assisted extraction protocol.

In China, Jiang Fructus aurantii (JFA) has attracted increasing interest as a famous traditional herbal medicine and valuable economic food for its valuable medicinal and industrial properties. In the current work, contrasted with conventional extraction techniques, natural flavonoids from JFA (naringin and neohesperidin) were extracted with remarkable effectiveness utilizing a sustainable deep eutectic solvents combined ultrasonic-assisted extraction (DESs-UAE) protocol. The optimal extraction capacity can be achieved by mixing 30 % water with a molar ratio of 1:3 for choline chloride and ethylene glycol, as opposed to the classical extraction solvents of 95 % ethanol, methanol, and water. Moreover, the DESs-UAE extraction programs were also systematically optimized employing Box-Behnken design (BBD) trials, and the eventual findings suggested that the best parameters were a 27 % water content in DES, a 16 mL/g liquid-solid ratio, a 72 min extraction time, and a 62 °C extraction temperature, along with the corresponding greatest contents of NAR (48.18 mg/g) and NEO (34.50 mg/g), respectively. Notably, by comparison with the pre-optimization data, the optimized DES extraction efficiency of flavonoids is markedly higher. Thereafter, the characterization of the solvents before and after extraction, as well as the differences between the four extraction solvent extracts, were compared using the FT-IR analyses. Furthermore, SEM results suggested that the penetration and erosion abilities of the plant cell wall of DES-1 were stronger than those of the other three traditional solvents, thus allowing more release of flavonoid compounds. In conclusion, the present research develops a straightforward, sustainable, and exceedingly efficient approach for the extraction of bioactive flavonoids from JFA, which has the potential to facilitate the efficient acquisition of active ingredients from TCM.

K+-Dependent Photocycle and Photocurrent Reveal the Uptake of K+ in Light-Driven Sodium Pump.

Engineering light-controlled K+ pumps from Na+-pumping rhodopsins (NaR) greatly expands the scope of optogenetic applications. However, the limited knowledge regarding the kinetic and selective mechanism of K+ uptake has significantly impeded the modification and design of light-controlled K+ pumps, as well as their practical applications in various fields, including neuroscience. In this study, we presented K+-dependent photocycle kinetics and photocurrent of a light-driven Na+ pump called Nonlabens dokdonensis rhodopsin 2 (NdR2). As the concentration of K+ increased, we observed the accelerated decay of M intermediate in the wild type (WT) through flash photolysis. In 100 mM KCl, the lifetime of the M decay was approximately 1.0 s, which shortened to around 0.6 s in 1 M KCl. Additionally, the K+-dependent M decay kinetics were also observed in the G263W/N61P mutant, which transports K+. In 100 mM KCl, the lifetime of the M decay was approximately 2.5 s, which shortened to around 0.2 s in 1 M KCl. According to the competitive model, in high KCl, K+ may be taken up from the cytoplasmic surface, competing with Na+ or H+ during M decay. This was further confirmed by the K+-dependent photocurrent of WT liposome. As the concentration of K+ increased to 500 mM, the amplitude of peak current significantly dropped to approximately ~60%. Titration experiments revealed that the ratio of the rate constant of H+ uptake (kH) to that of K+ uptake (kK) is >108. Compared to the WT, the G263W/N61P mutant exhibited a decrease of approximately 40-fold in kH/kK. Previous studies focused on transforming NaR into K+ pumps have primarily targeted the intracellular ion uptake region of Krokinobacter eikastus rhodopsin 2 (KR2) to enhance K+ uptake. However, our results demonstrate that the naturally occurring WT NdR2 is capable of intracellular K+ uptake without requiring structural modifications on the intracellular region. This discovery provides diverse options for future K+ pump designs. Furthermore, we propose a novel photocurrent-based approach to evaluate K+ uptake, which can serve as a reference for similar studies on other ion pumps. In conclusion, our research not only provides new insights into the mechanism of K+ uptake but also offers a valuable point of reference for the development of optogenetic tools and other applications in this field.

Novel trifunctional electrocatalyst of nickel foam supported Co2P/NiMoO4 heterostructures for overall water splitting and urea oxidation.

The process of electrocatalytic water splitting for hydrogen generation is significantly limited by sluggish kinetics of the anodic oxygen evolution reaction (OER). The efficiency of H2 electrocatalytic generation can be improved by reducing the anode potential or substituting urea oxidation reaction (UOR) for oxygen evolution process. Here, we report a robust catalyst based on Co2P/NiMoO4 heterojunction arrays supported on nickel foam (NF) for water splitting and urea oxidation. In the hydrogen evolution reaction in alkaline media, the optimized catalyst Co2P/NiMoO4/NF displayed a lower overpotential (169 mV) at a large current density (150 mA cm-2) compared to 20 wt% Pt/C/NF (295 mV@150 mA cm-2). In the OER and UOR, the potentials were as low as 1.45 and 1.34 V. These values surpass (for OER), or compare favorably to (for UOR), the most advanced commercial catalyst RuO2/NF (at 10 mA cm-2). This outstanding performance was attributed to the addition of Co2P, which has a significant effect on the chemical environment and electron structure of NiMoO4, while increasing the number of active sites and promoting charge transfer across the Co2P/NiMoO4 interface. This work proposes a high-performance and cost-effective electrocatalyst for water splitting and urea oxidation.

Greenhouse gas emissions from extractive industries in a globalized era.

The extractive industry consumes vast amounts of energy and is a major contributor to greenhouse gas (GHG) emissions. However, its climatic impacts have not yet been fully accounted for. In this study, we estimated the GHG emissions from extractive activities globally with a focus on China, and assessed the main emission drivers. In addition, we predicted the Chinese extractive industry emissions in the context of global mineral demand and cycling. As of 2020, GHG emissions from the global extractive industry had reached 7.7 billion tons of CO2 equivalents (CO2e), accounting for approximately 15.0% of the global anthropogenic GHG emissions (excluding GHG emissions from land use, land-use change, and forestry activities (LULUCF), with China being the largest emitter, accounting for 3.5% of global emissions. Extractive industry GHG emissions are projected to peak by 2030 or even earlier to achieve low-carbon peak targets. The most critical pathway for reducing GHG emissions in the extractive industry is to control emissions from coal mining. Therefore, reducing methane emissions from mining and washing coal (MWC) should be prioritized.

Modified stainless steel wires with superwettability for highly efficient in-tube solid-phase microextraction.

Construction of different surface wettability is meaningful for the interaction between the sorbent surface and target components. In the current study, four kinds of stainless-steel wires (SSWs) with different hydrophobic/hydrophilic property were prepared and used as the absorbents to enrich the target compounds with different polarity. Comparative extraction of six non-polar polycyclic aromatic hydrocarbons (PAHs) and six polar estrogens was carried out by in-tube solid phase microextraction (IT-SPME). The results showed that two SSWs with the superhydrophobic surfaces exhibited high extraction capacity to the non-polar PAHs with the superior enrichment factor (EF) in the range of 29-672 and 57-744, respectively. In contrast, the superhydrophilic SSWs demonstrated higher enrichment efficiency for the polar estrogens than other hydrophobic SSWs. On the basis of optimized conditions, a validated analysis method was established using six PAHs as model analytes for IT-SPME-HPLC. Acceptable linear ranges (0.5-10 µg L-1) and low detection limits (0.0056-0.32 µg L-1) were achieved using the superhydrophobic wire modified by perfluorooctyl trichlorosilane (FOTS). The relative recoveries spiked at 2, 5 and 10 µg L-1 in the lake water samples were in the range of 81.5%-113.7%. The relative standard deviation (RSD) of intraday (≤0.8%, n = 3) and interday (≤5.3%, n = 3) tests demonstrated the good extraction repeatability for the same extraction tube. Satisfactory repeatability for the preparation of extraction tubes (n = 3) was also obtained with the RSD values in the range of 3.6%-8.0%.

Smart Superhydrophobic Filter Paper for Water/Oil Separation and Unidirectional Transportation of Liquid Droplet.

Water/oil separation from their mixture and emulsion has been a prominent topic in fundamental research and in practical applications. In this work, a smart superhydrophobic membrane (SHP) was obtained by dipping an off-the-shelf laboratory filter paper in an ethanol suspension of trichloro (1H,1H,2H,2H-tridecafluoro-n-octyl) silane, tetraethyl orthosilicate, and titanium dioxide nanoparticles with different dimensions of 20 and 100 nm. The selection of membrane substrates was optimized including different quantitative and quantitative filter papers with different filtration velocity (slow, intermediate, and fast). The as-prepared SHP was demonstrated to be superhydrophobic and photosensitive, which was used in the separation of carbon tetrachloride and water from their mixture and emulsion. Moreover, orderly aligned micropores were formed for the modified superhydrophobic filter papers by using nanosecond laser. Unidirectional penetration was obtained for the UV-irradiated paper with a bored pore in the range of 50-500 µm in the systems of air/water and water/oil. This study may promote the understanding of unidirectional transportation of liquid droplet and facilitate the design of interfacial materials with Janus-type wettability.

Organic NIR-II dyes with ultralong circulation persistence for image-guided delivery and therapy.

Nanocarriers hold great promise for the controlled release of therapeutic payloads to target organs/tissues and extended duration of anticancer agents in the bloodstream. However, limited data on their in vivo pharmacokinetics and delivery process hamper clinical applications. Here we report a series of micellar nanocarriers self-assembled from new-generation thiophenthiadiazole (TTD)-based NIR-II fluorophores HLAnP (n = 1-4) for simultaneous bioimaging and drug delivery. The NIR-II HLA4P nanocarrier displays exceptional non-fouling performance, minimal immunogenicity, ultralong blood half-life, and high tumor accumulation even with different administration routes. When used as a drug carrier, HLA4P with encapsulated doxorubicin (DOX) realized accurate tumor targeting and continuous real-time in vivo NIR-II tracking of drug delivery and therapy, showing a sustained release rate, improved therapeutic effect, and diminished cardiotoxicity as compared to free DOX. This study provides a new perspective on the design of dual-functional NIR-II fluorophores for diagnostic and therapeutic applications.

Which is Better for Nanomedicines: Nanocatalysts or Single-Atom Catalysts?

With the rapid advancements in nanotechnology and materials science, numerous nanomaterials have been used as catalysts for nanomedical applications. Their design and modification according to the microenvironment of diseases have been shown to achieve effective treatment. Chemists are in pursuit of nanocatalysts that are more efficient, controllable, and less toxic by developing innovative synthetic technologies and improving existing ones. Recently, single-atom catalysts (SACs) with excellent catalytic activity and high selectivity have attracted increasing attention because of their accurate design as nanomaterials at the atomic level, thereby highlighting their potential for nanomedical applications. In this review, the recent advances in nanocatalysts and SACs are briefly summarized according to their synthesis, characterizations, catalytic mechanisms, and nanomedical applications. The opportunities and future scope for their development and the issues and challenges for their application as nanomedicine are also discussed. As far as it is known, the review is the systematic comparison of nanocatalysts and SACs, especially in the field of nanomedicine, which has promoted the development of nanocatalytic medicine.

2D/1D V2O5 Nanoplates Anchored Carbon Nanofibers as Efficient Separator Interlayer for Highly Stable Lithium-Sulfur Battery.

Quick capacity loss due to the polysulfide shuttle effects is a critical challenge for high-performance lithium-sulfur (Li-S) batteries. Herein, a novel 2D/1D V2O5 nanoplates anchored carbon nanofiber (V-CF) interlayer coated on standard polypropylene (PP) separator is constructed, and a stabilization mechanism derived from a quasi-confined cushion space (QCCS) that can flexibly accommodate the polysulfide utilization is demonstrated. The incorporation of the V-CF interlayer ensures stable electron and ion pathway, and significantly enhanced long-term cycling performances are obtained. A Li-S battery assembled with the V-CF membrane exhibited a high initial capacity of 1140.8 mAh·g-1 and a reversed capacitance of 1110.2 mAh·g-1 after 100 cycles at 0.2 C. A high reversible capacity of 887.2 mAh·g-1 is also maintained after 500 cycles at 1 C, reaching an ultra-low decay rate of 0.0093% per cycle. The excellent electrochemical properties, especially the long-term cycling stability, can offer a promising designer protocol for developing highly stable Li-S batteries by introducing well-designed fine architectures to the separator.

A bright NIR-II fluorescent probe for breast carcinoma imaging and image-guided surgery.

A novel bright near-infrared II (NIR-II, 1000-1700 nm) fluorescent probe with excellent water-solubility, superior photostability, and excellent in vitro and in vivo biocompatibility was facilely synthesized for in vivo biomedical imaging of xenograft breast tumor and chemically induced spontaneous breast carcinoma. To the best of our knowledge, it is the first time that the superior practical applications of this NIR-II probe in dimethylbenzanthracene (DMBA)-induced rat mammary carcinoma imaging and image-guided rat carcinoma surgery were demonstrated.

Correction: A bright NIR-II fluorescent probe for breast carcinoma imaging and image-guided surgery.

Correction for 'A bright NIR-II fluorescent probe for breast carcinoma imaging and image-guided surgery' by Xiaodong Zeng et al., Chem. Commun., 2019, DOI: .

Long noncoding RNAs C2dat1 enhances vascular smooth muscle cell proliferation and migration by targeting MiR-34a-5p.

Deregulated proliferation of vascular smooth muscle cells (VSMCs) is one common phenomenon of atherosclerosis progression. Long noncoding RNAs (lncRNAs) are one group of noncoding RNAs that play essential roles in many cell biological processes, including cell development, growth, and migration. However, the role of a novel calcium/calmodulin-dependent protein kinase type II subunit delta (CAMK2D)-associated lncRNA, CAMK2D-associated transcript 1 (C2dat1), in VSMCs is still uncovered. In this study, we showed that the expression level of C2dat1 was higher in coronary artery disease (CAD) tissues than in normal arterial tissues and the C2dat1 expression level was upregulated in the proliferating VSMC after being treated with PDGF-bb or TNF-α. In addition, we indicated that overexpression of C2dat1 promoted VSMC growth and enhanced proliferating cell nuclear antigen (PCNA) expression in VSMC. Moreover, ectopic expression of C2dat1 increased VSMC migration. Furthermore, we showed that elevated expression of C2dat1 suppressed microRNA-34a (miR-34a) expression and promoted sirtuin 1 (SIRT1) expression, which was a direct target gene of miR-34a. We demonstrated that the expression level of miR-34a was lower in CAD tissues than in normal arterial tissues and the expression of miR-34a was negatively correlated with C2dat1 expression. Restored expression of C2dat1 increased VSMC proliferation and migration through promoting SIRT1 expression. These data suggested that lncRNA C2dat1 might be a potential therapeutic target to promote VSMC growth and migration in CAD.

Jianpi Qingchang decoction regulates intestinal motility of dextran sulfate sodium-induced colitis through reducing autophagy of interstitial cells of Cajal.

AIM: To investigate the underlying effect of Jianpi Qingchang decoction (JQD) regulating intestinal motility of dextran sulfate sodium (DSS)-induced colitis in mice. METHODS: C57BL/6 mice were randomly divided into four groups: the control group, the DSS group, the JQD group, and the 5-aminosalicylic acid group. Except for the control group, colitis was induced in other groups by giving distilled water containing 5% DSS. Seven days after modeling, the mice were administered corresponding drugs intragastrically. The mice were sacrificed on the 15th day. The disease activity index, macroscopic and histopathologic lesions, and ultrastructure of colon interstitial cells of Cajal (ICC) were observed. The levels of tumor necrosis factor-alpha (TNF-α), interleukin (IL)-1ß, IL-10 and interferon gamma (IFN-γ), the expression of nuclear factor-kappa B (NF-κB) p65, c-kit, microtubule-associated protein 1 light chain 3 (LC3-II) and Beclin-l mRNA, and the colonic smooth muscle tension were assessed. RESULTS: Acute inflammation occurred in the mice administered DSS. Compared with the control group, the levels of IL-1ß, TNF-α, IL-10 and IFN-γ, the expression of LC3-II, Beclin-1 and NF-κB p65 mRNA, and the contractile frequency increased (P < 0.05), the expression of c-kit mRNA and the colonic smooth muscle contractile amplitude decreased in the DSS group (P < 0.05). Compared with the DSS group, the levels of IL-10 and IFN-γ, the expression of c-kit mRNA, and the colonic smooth muscle contractile amplitude increased (P < 0.05), the levels of TNF-α and IL-1ß, the expression of LC3-II, Beclin-1 and NF-κB p65 mRNA, and the contractile frequency decreased in the JQD group (P < 0.05). CONCLUSION: JQD can regulate the intestinal motility of DSS-induced colitis in mice through suppressing intestinal inflammatory cascade reaction, reducing autophagy of ICC, and regulating the network path of ICC/smooth muscle cells.

Jianpi Qingchang decoction alleviates ulcerative colitis by inhibiting nuclear factor-κB activation.

AIM: To investigate the therapeutic effect of Jianpi Qingchang decoction (JPQCD) on dextran sulfate sodium (DSS)-induced ulcerative colitis (UC) in mice. METHODS: C57BL/c mice were injected intragastrically with 5% DSS instead of drinking water for 7 d, and their body weight, diarrhea severity and fecal bleeding were monitored, while the mice in the control group were treated with standard drinking water, without DSS. After 7 d, the DSS drinking water was changed to normal water and the DSS group continued with DSS water. The control and DSS groups were given normal saline by intragastric injection. The 5-aminosalicylic acid (5-ASA) group was treated orally with 5-ASA at a dose of 100 mg/kg daily. The JPQCD group was treated orally with JPQCD at a dose of 17.1 g/kg daily. On day 14, the colon length was measured, the colorectal histopathological damage score was assessed, and protein levels of interleukin (IL)-1ß, IL-8 and tumor necrosis factor-alpha (TNF-α) in colon supernatants were measured by enzyme-linked immunosorbent assay. mRNA expression of IL-1ß, IL-8, TNF-α and nuclear factor-kappa B (NF-κB) was detected by real-time quantitative polymerase chain reaction. Western blotting was used to detect the protein expression of NF-κB and inhibitor of kappa B. RESULTS: Acute inflammation occurred in the mice administered DSS, including the symptoms of losing body weight, loose feces/watery diarrhea and presence of fecal blood; all these symptoms worsened at 7 d. The colons of mice treated with DSS were assessed by histological examination, and the results confirmed that acute inflammation had occurred, as evidenced by loss of colonic mucosa and chronic inflammatory cell infiltration, and these features extended into the deeper layer of the colon walls. The expression levels of IL-1ß, IL-8 and TNF-α in the DSS group were higher than those in the control group (P < 0.05), and the expression levels of IL-1ß, IL-8 and TNF-α in the JPQCD and 5-ASA groups were lower than those in the DSS group after treating with JPQCD and 5-ASA. Comparing with the DSS group, the mRNA level of IL-1ß, IL-8, TNF-α and NF-κB was significantly reduced by 5-ASA and JPQCD. The difference between JPQCD and 5-ASA groups was not statistically significant (P > 0.05). Comparing with the DSS group, due to using JPQCD and 5-ASA, significant suppression of activation in DSS-induced NF-κB and increased phosphorylation of IκB in mice with experimental colitis occurred (P < 0.05). The difference between the JPQCD group and the 5-ASA group was not statistically significant (P > 0.05). CONCLUSION: Activation of the NF-κB signaling pathway is inhibited by JPQCD, which shows the potential mechanism by which JPQCD treats UC.

Separation and characterization of bufadienolides in toad skin using two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography coupled with mass spectrometry.

Bufadienolides possess various bioactivities especially antitumor. Due to the high structural diversity, the separation of bufadienolides often suffers from coelution problem on conventional RP columns. In this work, an off-line two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography (2D-NPLC×RPLC) method was developed to separate and characterize bufadienolides in toad skin. Several RP and NP columns were evaluated with five reference bufadienlides. The XUnion C18 and XAmide columns exhibited superior chromatographic performances for bufadienlide separation, and were selected in RPLC and NPLC, respectively. RPLC was used in the second-dimension for the good compatibility with MS, while NPLC was adopted in the first-dimension. The orthogonality of the 2D-NPLC×RPLC system was investigated by the geometric approach using fifteen bufadienolide mixtures. The result was 49.6%, demonstrating reasonable orthogonality of this 2D-LC system. By combining the 2D-LC system with MS, 64 bufadienlides including 33 minor ones and 11 pairs of isomers in toad skin were identified. This off-line 2D-NPLC×RPLC allowed to solve the coelution problem of bufadienlides in one-dimension RPLC, and thus facilitated the identification significantly.

Impacts of wind stilling on solar radiation variability in China.

Solar dimming and wind stilling (slowdown) are two outstanding climate changes occurred in China over the last four decades. The wind stilling may have suppressed the dispersion of aerosols and amplified the impact of aerosol emission on solar dimming. However, there is a lack of long-term aerosol monitoring and associated study in China to confirm this hypothesis. Here, long-term meteorological data at weather stations combined with short-term aerosol data were used to assess this hypothesis. It was found that surface solar radiation (SSR) decreased considerably with wind stilling in heavily polluted regions at a daily scale, indicating that wind stilling can considerably amplify the aerosol extinction effect on SSR. A threshold value of 3.5 m/s for wind speed is required to effectively reduce aerosols concentration. From this SSR dependence on wind speed, we further derived proxies to quantify aerosol emission and wind stilling amplification effects on SSR variations at a decadal scale. The results show that aerosol emission accounted for approximately 20% of the typical solar dimming in China, which was amplified by approximately 20% by wind stilling.

Oxidovanadium(IV) sulfate-induced glucose uptake in HepG2 cells through IR/Akt pathway and hydroxyl radicals.

The insulin-mimetic and anti-diabetic properties of vanadium and related compounds have been well documented both in vitro and in vivo. However, the molecular basis of the link between vanadium and the insulin signaling pathway in diabetes mellitus is not fully described. We investigated the effects of reactive oxygen species (ROS) induced by oxidovanadium(IV) sulfate (VOSO4) on glucose uptake and the insulin signaling pathway in human hepatoma cell line HepG2. Exposure of cells to VOSO4 (5-50 µM) resulted in an increase in glucose uptake, insulin receptor (IR) and protein kinase B (Akt) phosphorylation and intracellular ROS generation. Using Western blot, we found that catalase and sodium formate, but not superoxide dismutase, prevented the increase of hydroxyl radical (·OH) generation and significantly decreased VOSO4-induced IR and Akt phosphorylation. These results suggest that VOSO4-induced ·OH radical, which is a signaling species, promotes glucose uptake via the IR/Akt signaling pathway.

Normal-pressure microwave rapid synthesis of hierarchical SnO2@rGO nanostructures with superhigh surface areas as high-quality gas-sensing and electrochemical active materials.

Hierarchical SnO2@rGO nanostructures with superhigh surface areas are synthesized via a simple redox reaction between Sn(2+) ions and graphene oxide (GO) nanosheets under microwave irradiation. XRD, SEM, TEM, XPS, TG-DTA and N2 adsorption-desorption are used to characterize the compositions and microstructures of the SnO2@rGO samples obtained. The SnO2@rGO nanostructures are used as gas-sensing and electroactive materials to evaluate their property-microstructure relationship. The results show that SnO2 nanoparticles (NPs) with particle sizes of 3-5 nm are uniformly anchored on the surfaces of reduced graphene oxide (rGO) nanosheets through a heteronucleation and growth process. The as-obtained SnO2@rGO sample with a hierarchically sesame cake-like microstructure and a superhigh specific surface area of 2110.9 m(2) g(-1) consists of 92 mass% SnO2 NPs and ∼8 mass% rGO nanosheets. The sensitivity of the SnO2@rGO sensor upon exposure to 10 ppm H2S is up to 78 at the optimal operating temperature of 100 °C, and its response time is as short as 7 s. Compared with SnO2 nanocrystals (5-10 nm), the hierarchical SnO2@rGO nanostructures have enhanced gas-sensing behaviors (i.e., high sensitivity, rapid response and good selectivity). The SnO2@rGO nanostructures also show excellent electroactivity in detecting sunset yellow (SY) in 0.1 M phosphate buffer solution (pH = 2.0). The enhancement in gas-sensing and electroactive performance is mainly attributed to the unique hierarchical microstructure, high surface areas and the synergistic effect of SnO2 NPs and rGO nanosheets.

Airborne fine particulate matter induces multiple cell death pathways in human lung epithelial cells.

Our group was the first one reporting that autophagy could be triggered by airborne fine particulate matter (PM) with a mean diameter of less than 2.5 µm (PM2.5) in human lung epithelial A549 cells, which could potentially lead to cell death. In the present study, we further explored the potential interactions between autophagy and apoptosis because it was well documented that PM2.5 could induce apoptosis in A549 cells. Much to our surprise, we found that PM2.5-exposure caused oxidative stress, resulting in activation of multiple cell death pathways in A549 cells, that is, the tumor necrosis factor-alpha (TNF-α)-induced pathway as evidenced by TNF-α secretion and activation of caspase-8 and -3, the intrinsic apoptosis pathway as evidenced by increased expression of pro-apoptotic protein Bax, decreased expression of anti-apoptotic protein Bcl-2, disruption of mitochondrial membrane potential, and activation of caspase-9 and -3, and autophagy as evidenced by an increased number of double-membrane vesicles, accompanied by increases of conversion and punctuation of microtubule-associated proteins light chain 3 (LC3) and expression of Beclin 1. It appears that reactive oxygen species (ROS) function as signaling molecules for all the three pathways because pretreatment with N-acetylcysteine, a scavenger of ROS, almost completely abolished TNF-α secretion and significantly reduced the number of apoptotic and autophagic cells. In another aspect, inhibiting autophagy with 3-methyladenine, a specific autophagy inhibitor, enhanced PM2.5-induced apoptosis and cytotoxicity. Intriguingly, neutralization of TNF-α with an anti-TNF-α special antibody not only abolished activation of caspase-8, but also drastically reduced LC3-II conversion. Thus, the present study has provided novel insights into the mechanism of cytotoxicity and even pathogenesis of diseases associated with PM2.5 exposure.