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Catalytic steam hydrogasification of coal is a direct method for methane production. Calcium looping concept is usually used in coal gasification process for in-situ carbon dioxide removal and heat supply. In this paper, a new process combining catalytic steam hydrogasification and calcium looping was proposed and investigated using a self designed instantaneously feeding reactor under high-temperature and pressurized conditions. The effects of operation conditions (including hydrogen concentration with a range of 0–50 vol%, gasification pressure with a range of 0.1–3.5 MPa, gasification temperature with a range of 700–800 °C, and gasification-calcination cycle number up to six) on the performance of the new process have been studied. The results show that: (i) increasing H2 concentration is beneficial to methane products; (ii) high temperature and low pressure are not conducive to methane production and carbon dioxide capture as well as the self-sustained heat supply in gasifier; (iii) the methane content and carbon conversion can be maintained at 30–40 vol% and 75–80% for the durability tests. According to the performance of gas products, 750 °C 3.5 MPa and Ca/C = 0.5 are suggested for the new process. In addition, the gasification reactivity can be affected by the Ca–K-Char interaction as indicated by the XRD, FT-IR and SEM-EDX analysis.

Conventional semiconductor photocatalysts produce superoxide and hydroxyl radicals as the major reactive oxygen species (ROS). Here, we report that Ag/Ag3PO4 catalyst efficiently generates singlet ...

Silver(I) salts were found active in the borylation and sulfenylation of aryl iodides under visible light irradiation. The optimized borylation protocol using AgF did not need any additive, operated under very mild conditions, and well tolerated a broad scope of substrates and boron sources. Formation of Ag(0) single atoms (AgSAs) during the borylation reactions was examined using high-angle annular dark field aberration-corrected scanning transmission electron microscope (HAADF AC-STEM) and electron paramagnetic resonance (EPR). The activities of the silver(I) salts were affected by the anions and could be associated with their abilities in formation of AgSAs during the reactions. Kinetic studies showed that the deiodination rate was linearly correlated with the loading of AgSAs, and hence AgSAs were the true catalytic centers for the 1e −-reduction of the C-I moieties. The oxidation state of AgSAs kept 0 in both the resting and the working states. A “work-in-tandem” mechanism involving AgSAs as the catalytic centers and AgNPs as the light absorber to achieve the borylation of aryl iodides under visible light irradiation is proposed. The current approach not only provides an alternative system for borylation and sulfenylation of aryl iodides, but also reveals a new activity of silver(I) salts involving AgSAs under visible light irradiation.

Four representative pretreatment methods, water washing (WW), acid washing (AW), dilute acid hydrolysis (DH), and microwave assisted organosolv pretreatment (MOP), were adopted to alter eucalyptus ...

Silica dust mainly attacks alveolar macrophages (AMs). The apoptosis of AMs is correlated with the progress of silicosis. Our previous study showed that autophagic degradation was blocked in AMs from silicosis patients. However, the effects of nicotine on AM autophagy and apoptosis in silicosis are unknown. In this study, we collected AMs from twenty male workers exposed to silica and divided them into observer and silicosis patient groups, according to the tuberous pathological changes observed by X-ray. The AMs from both groups were exposed to nicotine. We found increased levels of LC3, p62, and cleaved caspase-3, decreased levels of LAMP2, and damaged lysosomes after nicotine stimulation of the AMs from both groups. We also found that the autophagy inhibitor 3-methyladenine (3MA) inhibited nicotine-induced apoptosis in the AMs. Furthermore, 3MA reversed both the nicotine-induced decrease in Bcl-2 and the increase in Bax in both groups. These results suggest that nicotine may induce apoptosis by blocking AM autophagic degradation in human silicosis.

Chemical looping partial oxidation of methane (CLPOM) coupled with carbon dioxide splitting process was proposed in this work to achieve high H2/CO ratio syngas and CO production simultaneously. Manganese ferrite (MnFe2O4) oxygen carrier with a spinel structure was prepared by using a co-precipitation phase inversion method for this methane-carbon dioxide reaction system. The reaction performance of oxygen carrier was investigated in fixed bed reactor combined with the analytical methods of XRD, TPR, H2-TG and XPS. The results revel that spinel structure MnFe2O4was successfully prepared and Fe is the main active spices to release lattice oxygen. TG analysis confirms that 43.3% of lattice oxygen can release from MnFe2O4 in H2 atmosphere with highest release rate 0.4%/min at 721 °C. The maximum conversion of CH4 and CO2 are 63% and 99% achieved in CLPOM coupled with CO2 splitting process and temperature makes a positive effect on the reaction process. Moreover, the reaction stability of MnFe2O4 oxygen carrier are verified in 10 cycles reaction of CLPOM coupled with CO2 splitting with the reaction path MnFe2O4 → (FeO)0.798-(MnO)0·202/FeO → MnFe2O4. Moreover, The MnFe2O4 oxygen carriers with different reduction stages were analyzed by XPS to reveal lattice oxygen migration mechanism, which indicates that the bulk lattice oxygen of oxygen carrier gradually dissociated and migrated to the outer surface in reaction process where reacts directly with methane or converts to oxygen adsorption OII. The valence of Mn has not changed in the whole reaction process, whereas, Mn species forms the synergistic effect with Fe to improve the conversion of CH4 and CO2, promoting the oxidization of Fe2+ to Fe3+ in CO2 atmosphere. MnFe2O4 oxygen carrier is a promising candidate for the CLPOM coupled with CO2 splitting process.

Biomass chemical looping gasification (BCLG) is a novel and promising technology for syngas production, in which lattice oxygen in oxygen carriers (OCs) reacts with biomass. OCs can continuously su...

Background and aims Although serum lipids are widely accepted as independent predictors of myocardial infarction (MI), there is insufficient evidence for associations of changes in lipid levels with MI. The present study aimed at investigating the associations between changes in lipids and incidence of MI in people without lipid-lowering therapy. Methods 64,031 Chinese participants (mean age: 53.42 ± 11.95 years) without previous MI were enrolled in the study. The participants were divided into four categories based on quartiles of lipid changes. Multivariable Cox regression models were used to calculate hazard ratios (HRs) and 95% confidence intervals (CIs) for MI. Results During a median follow-up of 7.03 years, 599 individuals developed MI. After adjustment for covariates, increased total cholesterol (TC), increased low-density lipoprotein cholesterol (LDL-C), increased non-high-density lipoprotein cholesterol (non-HDL-C), and decreased high-density lipoprotein cholesterol (HDL-C) were associated with elevated risk of MI, with HRs (95% CIs) in the highest quartile group compared with the lowest quartile group of 1.56 (1.21–2.01), 1.96 (1.49–2.57), 1.95 (1.52–2.50), and 0.69 (0.53–0.90), respectively. However, changes in triglyceride (TG) were not associated with MI risk (p = 0.8030). Conclusions Changes in levels of TC, LDL-C, non-HDL-C, and HDL-C, but not TG, were associated with risk of MI. Early detection and control of lipid levels may be beneficial and necessary for young people and those with healthy lipid levels at baseline.

The aim of this study was to investigate the effect of torrefaction severity and ratio of oxygen carrier to feedstock on syngas production and tar removal during chemical looping gasification of eu...

Synthesis gas production via chemical-looping partial oxidation (CLPO) of methane reduces operating cost and likely avoids carbon dioxide emissions. Previous studies exhibit La0·7Sr0·3FeO3 (LSF) a good high-temperature oxygen carrier, but not being applicable in intermediate-temperature CLPO processes. This work proposes a CuO modified LSF (xCuO/LSF, x = 2,5,10,15) for enhancing the reactivity of oxygen carriers at relatively low temperatures. Characterization methods, including N2 physisorption, ICP-OES, H2-TPR, XRD and XPS, are implemented to determine properties of xCuO/LSF. Fixed-bed experiments determine the best candidate under 750 °C is 10CuO/LSF. The methane conversion rate of 10CuO/LSF is more than 3 times compared to that of unmodified LSF and the concentration of syngas increases by 375% with the H2/CO molar ratio of about 2.5. The regenerability of 10CuO/LSF proves to be good. This study provides a promising and simple way to lower the operating temperature of the CLPO process, likely leading a considerable energy saving.

The Z-scheme BiVO4/Ag/Ag2S photocatalyst was fabricated via a two-step route. The as-prepared samples were characterized by XRD, FE-SEM, HRTEM, XPS and UV-vis diffuse reflectance spectroscopy. The results of PL and photocurrent response tests demonstrate that the ternary BiVO4/Ag/Ag2S composites had a high separation and migration efficiency of photoexcited carriers. As a result, the ternary photocatalyst exhibits enhanced photocatalytic activity for decomposing Rhodamine B (RhB) under LED light (420 nm) irradiation. The results of trapping experiments demonstrate both h+ and ˙OH play crucial roles in decomposing RhB molecules. Additionally, the energy band structures and density of states (DOS) of BiVO4 and Ag2S were investigated via the density functional theory (DFT) method. Finally, a Z-scheme electron migration mechanism of BiVO4 → Ag → Ag2S was proposed based on the experimental and calculated results.

Iron and nickel-based catalysts over an olivine support were prepared by different methods (thermal fusion (TF) and wetness impregnation (WI)), and the effect of steam reforming of phenol and naphthalene on those catalysts was tested. The structure of catalysts synthesized by the TF method exhibited obvious differences compared with the WI method. During the thermal fusion process, part of Fe and Ni was migrated into the olivine framework to form (Mg,Fe) Fe2O4 and Ni2SiO4(NiFe2O4), respectively. In this structure, Fe and Ni acted as active metal, and Si, Mg, O acted as dispersed phases, so Fe and Ni can be dispersed more uniformly and exhibit more stable catalytic activity. However, The Fe and Ni presented as Fe2O3 and NiO–MgO in the wetness impregnation process which was easily sintered and consumed duo to attrition during the catalytic reaction. The catalysts prepared by the two methods both performed well for phenol steam reforming (Fe-containing catalysts reached more than 93% and Ni-containing catalysts reached more than 99%) and carbon deposition resistance (carbon deposition rates were both lower than 7%), while the carbon deposits from the steam reforming of naphthalene were difficult to eliminate by steam. After analysis, it was found that the carbon deposits from phenol catalytic cracking was mainly Cα which was easy to react with steam, and that those from naphthalene were mainly Cβ and Cγ which had poor reactivity.

To meet the increasing wastewater treatment demand while minimizing the land footprint of the treatment systems and plants, more efficient and compact processes are needed. The circulating fluidized bed bioreactor (CFBBR) has been proven to achieve high levels of biological nutrient removal. Past studies at the lab and pilot scale achieved 94% COD removal and 80% nitrogen removal at HRT's of 2-4 h. A collaborative project between Western University and the Guangzhou Institute of Energy Conversion (GIEC), in Guangzhou, China, further explored the treatment of municipal wastewater with the CFBBR. A pilot CFBBR, with aerobic and anoxic columns for nitrification and denitrification, was constructed at the GIEC for in-situ treatment of septic tank effluent from a residential building. Due to high concentrations of ammonia (NH4-N), the wastewater had a COD/N ratio of 2-3. Thus, operating at a longer HRT and supplementing COD, in the form of glucose, was necessary to achieve a high nitrogen removal efficiency. The system was run both with and without supplemental COD at HRT's between 16 and 21 h, treating approximately 1000-1270 L/d. Overall, a COD removal efficiency of at least 92%, ammonia removal of 97%, and nitrogen removal of 82% was achieved. The CFBBR system achieved an effluent with BOD and NH4-N concentrations both below 5 mg/L, a NO3-N concentration below 15 mg/L, and a total nitrogen concentration below 25 mg/L. The compact design of this pilot-CFBBR, coupled with its high BNR performance make it an excellent option for decentralized treatment of urban wastewaters.

As a novel biomass gasification technology, chemical looping gasification (CLG) could in situ catalytically crack biomass tar by oxygen carrier (OC). This study compares the reactivity of different OCs (Al₂O₃, Fe₂O₃, NiO, NiO+Fe₂O₃, and NiFe₂O₄) to crack a biomass tar model compound (toluene) and preliminarily explores the reaction mechanisms of toluene cracked by NiFe₂O₄ OC. Among five OCs, NiFe₂O₄ with a homogeneous Fe/Ni dispersibility shows the best reactivity for toluene cracking with a toluene conversion and H₂ yield of 96.83% and 0.91 L/g, respectively. Additionally, on the basis of the dispersibility of active sites on the OC sample surface, the reactivity of the other four OCs to crack toluene shows the sequence NiO+Fe₂O₃ > Fe₂O₃ > NiO ≫ Al₂O₃. A large amount of carbon deposition, including amorphous carbon and graphitized carbon, is generated during toluene catalytic cracking, while the addition of steam significantly eliminates the carbon deposition. The NiFe₂O₄ OC shows a dual-function of in situ oxidation–catalysis during toluene cracking. A mechanism of four steps is proposed for the toluene cracking on OCs: (I) toluene cracking at high temperature, (II) reduction of OC, (III) generation of amorphous carbon deposition and (III′) formation of graphitized carbon, and (IV) elimination of carbon deposition.

Softwood is an abundantly available lignocelloluse feedstock which can be converted into chemical and liquid fuels via sugar-based platform molecules. However, cost-effective release of pyrolytic sugars from softwood is considerably hindered by the biomass recalcitrance related to its compositions and structures as well as the catalytic effect of alkali and alkaline earth metals. In order to address these challenges, a novel biorefinery based on H2SO4 assisted organosolvolysis of softwood (e.g. pine wood) in high boiling organic solvents coupled with subsequent fast pyrolysis is proposed. The experimental results demonstrated that H2SO4 assisted organosolvolysis could effectively deconstruct pine wood into pentose, organosolv lignin, cellulose-rich fraction, and simutaneously transfer alkali and alkaline earth metals to solutions, thus improving the yields of platform chemcials (levoglucosan and phenols) in subsequent fast pyrolysis. Moreover, different high boiling solvents showed obviously distinct performance for the deconstruction of pine wood and removal of alkali and alkaline earth metals, thus resulting in different yields of platform chemcials in the subsequent fast pyrolysis. The rank order of these solvents which are beneficial for improving the yield of pyrolytic sugars from pine wood was ethylene glycol > glycerin + ethylene glycol (mass ratio of 1:1) > glycerin > γ-valerolactone. The yield of levoglucosan increased drastically from 3.53 wt% of raw pine wood to 27.19 wt% of cellulose-rich fraction pretreated by ethylene glycol with 1 wt% H2SO4. It was found that the yield of levoglucosan from fast pyrolysis of feedstocks was subjecetd to the mutual effect of normalized total alkali and alkaline earth metals’ valencies and severity of delignification. These findings help to provide a simple and efficient process to selective production of platform chemicals from highly recalcitrant biomass.

Fast pyrolysis is a comparable technology with enzyme or acid hydrolysis for saccharification of biomass. The low yield of levoglucosan and the formation of inhibitors to biocatalysts from lignocellulose hamper the fermentable utilization of pyrolysate. In this study, aiming to enhance the production of levoglucosan, dilute alkali pretreatment was performed prior to fast pyrolysis of corncobs. The yield of levoglucsoan from pretreated corncobs was significantly improved (34.8%) as compared to that from un-treated corncobs (3.0%), which was mainly attributed to the removal of alkaline and alkaline earth metals as well as lignin fraction by NaOH pretreatment. Conversely, NaOH pretreatment suppressed the formation of acids (from 11.1 to 2.2%), furans (from 2.5 to 2.0%), ketones (from 15.7 to 9.8%) and phenols (from 4.8 to 1.3%), which were common inhibitors to the biocatalysts. Accordingly, NaOH pretreatment facilitated further selective conversion of biomass in fast pyrolysis and made the pyrolysate more fermentable.

Chemical looping gasification (CLG) of sewage sludge (SS) using calcined copper slag as an oxygen carrier (OC) represents a novel approach for achieving the comprehensive use of two wastes (SS and copper slag), where the SS is converted into syngas through the oxidation of calcined copper slag. The effect of the calcined temperature on the reactivity of copper slag was first studied. The results show that the copper slag calcined at 1100 °C (1100CS) exhibits excellent performance for SS gasification. Using 1100CS as an OC, the effect of the mass ratio of OC and SS (OC/SS), steam content, oxygen source and cycle number on the SS CLG were investigated in detail in a fixed bed reactor. OC/SS and steam content are determined at 5 and 33.33% for obtaining a relatively high carbon conversion and an acceptable energy recovery during the SS CLG, respectively. The 1100CS is similar to steam, which can provide an oxygen source for SS conversion, and it can catalyze the cracking of tar. The conversion of SS undergoes a slight increase with the cycle number due to the prolongation of the gas-solid mean residence time (Rt) and the deposition of alkali or alkaline earth metals on the surface of the OC particles. Phosphorus eventually appears in the form of water-soluble phosphate during the SS CLG, benefiting its recovery. Thus, CLG with 1100CS as an OC is one of good option for sludge treatment.

Chemical looping steam reforming (CLSR) is a novel technology for hydrogen production using metal oxide as an oxygen carrier (OC). During the CLSR, the OC (MeO) is first reduced to the final state ...

The double perovskite oxides (DPOs) LaSrFe2-xCoxO6 (x = 0, 0.2, 0.4, 0.6, 0.8) were investigated as oxygen carriers for the chemical looping steam methane reforming (CL-SMR). The fresh oxides were prepared by micro-emulsion method and their physical and chemical properties were characterized by X-ray diffraction, H2-temperature programmed reduction and X-ray photoelectron spectroscopy technologies. Meanwhile, isothermal reactions for methane reforming and steam splitting were carried out in a fixed-bed reactor to determine the influences of Co-substitution on the reactivity of LaSrFe2-xCoxO6. The substitution of metal Co has no obvious effect on the crystal structure of double perovskite, but induces a certain degree of Fe/Co disorder generating oxygen vacancies and/or higher oxidation states of metal cations. Synergistic interaction between surface metal ions, such as (Fe4+/Fe5+-O2--Co2+) and (Fe3+-O2--Co3+), plays a positive effect for the dissociation of methane. The activity may be more likely to be associated with the active oxygen species in connection with Co species on the DPOs surface and abundant of syngas was generated due to the concordant of methane dissociation with the lattice oxygen diffusion. Comprehensively considered, an optimal range of the degree of Co substitution is x = 0.4–0.6 for LaSrFe2-xCoxO6, probably converting 70% of CH4 into CO and H2 with molar ratio around 2:1. At the reduced states, the ability of DPOs for steam splitting is primarily associated with the oxygen vacancies after oxygen consumption. The substitution of metal Co slightly enhances the hydrogen production capacity and resistance to carbon formation, achieving the average hydrogen yields at 2.89–3.33 mmol/g oxygen carrier and 1.46–1.61 wt% of carbon depositions.

Fast pyrolysis, which is comparable with the enzyme or acid hydrolysis, should be considered for further development for fermentable levoglucosan (LG) production. This manuscript offers a broad review of the current status and future research perspectives of LG and its hydrolysates production from lignocellulosic biomass by fast pyrolysis for fermentation. The utilization, distribution and formation paths of LG from cellulose are presented. In consideration of the complexity of cellulose structure and lignocellulosic components, the influence of the major individual components (cellulose, hemicellulose, lignin and ash) and the structural properties (particle size, degree of polymerization and crystallinity) on the LG formation are reviewed. Aiming to further improve the yield of LG and the fermentability of pyrolysate, a number of pretreatment methods (e.g. hot-water pretreatment, acid pretreatment, acid impregnation) prior to fast pyrolysis, hydrolysis of LG and detoxification before fermentation, and microbial production of valuable products are also discussed in detail. At last, a brief conclusion for the challenge in this topic is provided. The low content of LG and the presentence of inhibitors to biocatalysts in the pyrolysate of lignocelluloses hamper the fermentable utilization of pyrolytic sugars, which need further investigation and improvement to make this process feasible.

Chemical-looping steam methane reforming (CL-SMR) is a novel technology for syngas and hydrogen production without purification process. A series of three-dimensionally ordered macroporous (3DOM) LaFe1−xNixO3 (x = 0.05, 0.1, 0.15, 0.2, 0.25, 0.3) perovskite-type oxides were synthesized using the polystyrene colloidal crystal templating method. The structural and physico-chemical properties of the obtained oxides were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Brunauere-Emmette-Teller (BET) surface area technologies. The structure-reactivity relationships and effects of Ni-substitution on the improvement of reactivity and resistance to carbon formation were investigated in a thermo-gravimetric analyzer and a fixed-bed reactor. It was found that the as-prepared oxides obtained standard perovskite structures and the well-ordered skeleton was surrounded with uniform close-packed macroporous windows. Ni-substitution improved the ability for oxygen supply but simultaneously enhanced the methane dissociation. While the openness channel and large surface area of 3DOM perovskite allowed low mass-transfer resistances and provided high active sites for reaction. Complicated factors synergistically affected the reactivity and an optimal value for Ni-substitution is confirmed with x = 0.1 by comprehensively considering from the points of reactivity, resistance to carbon formation, as well as hydrogen generation capacity. During the following successive redox reactions, 3DOM LaFe0.9Ni0.1O3 exhibited good regenerability and thermo-stability probably converting 90% of CH4 into syngas in methane reforming stage and generating ∼210–220 ml hydrogen in steam splitting stage.

The longitudinal association between glycated hemoglobin (HbA1c) and different courses of depressive symptoms is understudied. This study aimed to identify different trajectories of depressive symptoms and investigate the relation of HbA1c with the risk of increasing and high-stable depressive symptoms. In the China Health and Retirement Longitudinal Study, depressive symptoms were measured using the 10-item Center for Epidemiological Studies-Depression scale in three visits (years: 2011, 2013 and 2015) among 9804 participants (mean age 60.0 ± 9.0 years). Group-based trajectory modeling was used to identify trajectories of depressive symptoms. HbA1c was measured at baseline and categorized five groups according to the respective quintile. Multinomial logistic regression was fitted to examine this relationship. Four distinct trajectories of depressive symptoms were identified: low symptoms (n=6401, 65.29%); decreasing symptoms (n=1362, 13.89%); increasing symptoms (n=1452, 14.81%); and high symptoms (n=1452, 14.81%). Adjusting for demographic, health-related, and cognitive factors, the risk ratio (95% confidence interval) pertaining to the highest HbA1c (Quintile 5) for decreasing, increasing, and high symptoms of depression versus low symptoms was 1.01 (0.82-1.25), 1.12 (0.92-1.36), and 1.39 (1.04-1.86) compared with the lowest HbA1c (Quintile 1), respectively. We observed a J-shaped relationship between HbA1c and high depressive symptoms, with the lowest risk at a HbA1c concentration of 5.0%. In summary, in this large population-based cohort, high levels of glycated hemoglobin concentrations were associated with a higher risk of increasing and high-stable symptoms of depression.

Chemical looping methane reforming (CLMR) is a promising technology for syngas generation by designing an oxygen carrier to partially oxidize methane into mixed gases with expected H2/CO ratio. The major challenge is the development of oxygen carriers with high reactivity, good selectivity, and excellent recyclability. We investigated a novel interstitial doped perovskite as an oxygen carrier to regulate the oxidation activity and demonstrated that Mg ions that interstitial entering into the crystal lattice of perovskite can improve the activation of methane greatly without any change of the crystal structure. According to the results of XPS and H2-TPR, Mg ions also reduced the electron binding energy of oxygen on the sample surface and increased the migration rate of lattice oxygen. Compared with LSFC and Li-LSFC, the interstitial doping Mg-LSFC exhibited higher average methane conversion up to 98.66%, accompanying with 78.15% hydrogen content. Furthermore, the average yield of hydrogen of Mg-LSFC increased from 1.60 ml to 2.25 ml per 1 ml of methane when 0.02 g/min water participated in the reaction. Besides, the stability of Mg-LSFC was also proved by thermogravimetric experiments and fixed bed pulse experiments. Based on the experiment results, the reaction mechanism for methane activation was discussed to further providing a pathway to effectively enhance the hydrogen-rich syngas generation.

Chemical looping gasification (CLG) of lignite by using hematite oxygen carrier is performed to achieve high purity synthesis gas. The oxygen carrier reaction performance as well as the effects of temperature and lignite/oxygen carrier ratio on the syngas evaluation are investigated by TG and fixed bed reactor coupling with various analytical methods. The experimental results reveal that the hematite oxygen carrier consisting primarily of Fe2O3, SiO2 and Al2O3 presents three H2 reduced peaks at 472.59 °C, 634.17 °C and 849.01 °C respectively, corresponding to the crystal form transition from Fe2O3 to Fe. Lignite pyrolyzes preferentially to generate intermediates then further reacts with oxygen carrier to produce synthesis gas in CLG process, following the oxygen carrier reaction path of Fe2O3 → Fe0.963O → Fe2O3. Oxygen carrier plays a key role in promoting lignite conversion to synthesis gas in CLG process owing to the lattice oxygen shifting reactions equilibrium to the direction of syngas production. Excessive lattice oxygen is beneficial to CLG reaction until the L/O ratio reaches to 4/6 with the limitation of heat and mass transfer in reaction system. However, the minimum value of O/L is 2/8, which ensures the oxygen carrier makes obvious promotion effect in reaction process. High temperature improves synthesis gas yield and carbon conversion by enhancing endothermic reactions in CLG process. The hematite oxygen carrier recovers main crystalline phase after the CLG process without serious sintering.

Adsorption and desorption of phosphorus (P) at sediment-water interface is one of the key processes of biogeochemical cycling of P in lakes. Thus, adsorption of phosphate by sediments from Lake Dianchi, a eutrophic lake, was investigated in this study. Importantly, the influence of dissolved organic matter (DOM) with fulvic acid (FA) as a representative example on these processes was further studied. The results showed that the presence of FA in the solution did not change the tendency of phosphate adsorption by sediments from Lake Dianchi. Compared with Freundlich equation, Langmuir model fitted better in describing the adsorption isotherms. And the pseudo-second-order kinetic model predicated well the adsorption kinetics for adsorption of phosphate by sediments. Under low concentrations of phosphate, FA promoted desorption of phosphate adsorbed on the sediments. However, adsorption behaviors including capacity and efficiency would be enhanced by presence of FA under high concentrations of phosphate. Based on adsorption thermodynamics, temperature and DOM (FA in this study) were two most important factors for adsorption of phosphate by sediments. Adsorption of phosphate on sediments was a spontaneous endothermic reaction process, which was a chemical-physical process rather than a simple physical adsorption. The influence of FA on the adsorption of phosphate by sediments was closely related with characteristics of sediments such as contents of Fe-Al oxides and organic matter. Aggressive results showed that increasing DOM due to algal blooming was likely an important way for dominant algae to maintain the nutrients such as P in lakes.

In this study, ball milling and ionic liquid pretreatments were utilized to alter cellulose structure prior to fast pyrolysis and enzymatic hydrolysis. The variations in the products distribution of cellulose fast pyrolysis, and their dependence on the structure of cellulose, and the temperature of fast pyrolysis were illustrated. Fast pyrolysis of pretreated cellulose yielded more levoglucosan than crystalline cellulose (14.7%) at 300 °C. Nevertheless, the levoglucosan achieved higher yield (64.3%) from crystalline cellulose at 400 °C. At last, a comparison between fast pyrolysis and enzymatic hydrolysis for cellulose saccharifaction was made. Fast pyrolysis was a promising alternative to liberate levoglucosan from cellulose. Further investigation and development were required to maximize the levoglucosan production.

The objective of this study was to selectively coproduce anhydrosugars and furfural from the fast pyrolysis of biomass by H2SO4 impregnation. The pyrolysis behaviors of raw and H2SO4-impregnated corncobs, cellulose and xylan were systematically studied by a thermogravimetric analyzer (TGA) and commercial pyroprobe reactor. The results demonstrate that H2SO4 impregnation can reduce the formation of char and drastically improve the yield of anhydrosugars and furfural. The maximum yields of levoglucosan (38.45 wt% based on cellulose), furfural (19.18 wt% based on hemicellulose) and xylosan (9.49 wt% based on hemicellulose) were obtained by fast pyrolysis of corncobs impregnated with 2.75 wt% H2SO4. By comparing the product distributions from fast pyrolysis of H2SO4-impregnated cellulose, xylan, and raw and demineralized corncobs, it is concluded that H2SO4 can act as an inhibitor to suppress the catalytic functions of structural alkali and alkaline earth metals (AAEM) to improve the yield of anhydrosugars, and H2SO4 can also act as a catalyst to accelerate the dehydration of hemicellulose to form more furfural. It is speculated that H2SO4 could first react with structural AAEM in lignin to form lignosulfonates (e.g., potassium lignosulfonate), thus reducing the catalytic functions of structural AAEM during fast pyrolysis of corncobs. These findings provide a simple and efficient method for the selective coproduction of anhydrosugars and furfural from waste biomass.

Well dispersed CuO nanoflakes were successfully achieved via a fast and self-heating route. The physical properties of the as-prepared products were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), nitrogen adsorption-desorption measurements, transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Meanwhile, the catalytic activity and the catalytic advantage of CuO nanostructures are discussed with the help of first-order kinetics investigation for methylene blue degradation. It is found that self-heating in the reaction mixture and formation of cellular CuO network fully filled with oxygen bubble are mainly responsible for synthesis of CuO nanoflakes. Meanwhile, the as-obtained CuO nanoflakes possessed high specific surface area and exhibited high catalytic characteristics with wet hydrogen peroxide oxidation in methylene blue solution. The present work is likely to be favorable for taking full advantage of the catalytic activity of CuO nanostructures with high specific surface area for the wet hydrogen peroxide oxidation of dyes.

Chemical looping reforming (CLR) coupling with chemical looping hydrogen (CLH) was proposed to reform biomass based pyrolysis gas and achieve high purity H2 by using Fe/Ni/Al oxygen carriers derived from layered double hydroxide (LDH) precursors. The crystal form, morphology and reactivity of oxygen carriers were characterized by various analysis methods. The chemical looping reaction process was investigated in a fixed bed reactor. The experimental results exhibited that Fe0.99Ni0.6Al1.1O4 high dispersed oxygen carrier was synthesized. Moderate lattice oxygen releasing rate 0.00175 wt%/s and escape ratio 95.14% were achieved by the mixed oxygen carrier with Fe/Ni ratio of 3/1. Ni had positive effect on lattice oxygen escape ratio of oxygen carrier while Fe contributed to improve the instantaneous lattice oxygen releasing rate. Furthermore, the CH4/CO2 in biomass based pyrolysis gas was eliminated via CLR process based on the metal catalytic effect of oxygen carrier. The highest CH4 conversion 98.26% and CO2 conversion 71.92% were obtained in CLR process accompanying with the reduction of Fe0.99Ni0.6Al1.1O4 to Fe/Ni alloy. Additionally, H2 with 96.56% purity was achieved in CLH process with the conversion of Fe/Ni alloy to Fe3O4. The H2 instantaneous generation rate increased sharply to the maximum value 34.70 ml/min and then declined gradually. Ni0.6Fe2.4Al1.1O4 new high dispersed compound was generated in the regeneration stage with similar structure to fresh sample and more active Fe species content. Though the particle size of oxygen carrier tended to decline after whole reaction process, the porous structure was still reserved.

Essential metal elements (EMEs) have essential roles in neurological development and maintenance of human homeostasis. We performed a case-control study to explore association between the risk of autism spectrum disorder (ASD) and the 11 EMEs [Calcium (Ca), potassium (K), magnesium (Mg), sodium (Na), manganese (Mn), selenium (Se), cobalt (Co), Molybdenum (Mo), copper (Cu), zinc (Zn), and iron (Fe)] in serum. Ninety-two autistic subjects (cases) and age-sex-matched healthy subjects (controls = 91) from Beijing, China were recruited. In addition, totally 109 mothers of recruited children participated in this study. ICP-AES and ICP-MS were applied to determine the concentration of 11 EMEs in serum. The concentrations of Ca, K, and Mg were significantly higher in the cases than in the controls (OR [95% CI]: 1.031 [1.006-1.058] for Ca; 1.081 [1.046-1.118] for K; 1.161 [1.012-1.331] for Mg), while the concentrations of Zn and Cu were significantly lower (0.997 [0.995-0.999] for Cu; 0.996 [0.992-1.000] for Zn). Clear dose-response relationships between EMEs concentrations and the risk of ASD, as well as the correlation between EME concentrations and the severity of ASD were observed for most of the above EMEs. Six and seven specific correlated pairs between mothers and children were found in the cases and controls separately. The overall profiles of the EMEs were changed in the cases as compared to the controls. This study suggested that the higher levels of Ca, K, and Mg and lower levels of Zn and Cu may be associated with an elevated risk of ASD.

Silicosis is characterized by pulmonary interstitial fibrosis that arises as a result of chronic exposure to silica. The few available treatments only delay its progression. As α-lipoic acid (ALA) has been shown to have various beneficial effects, including mitoprotective, antioxidant, and anti-inflammatory effects, we hypothesized that it may exhibit therapeutic effects in pulmonary fibrosis. Therefore, in the present study, we used a murine model of silicosis to investigate whether supplementation with exogenous ALA could attenuate silica-induced pulmonary fibrosis by improving mitochondrial function. ALA was administered to the model mice via continuous intragastric administration for 28 days, and then the antioxidant and mitoprotective effects of ALA were evaluated. The results showed that ALA decreased the production of reactive oxygen species, protected mitochondria from silica-induced dysfunction, and inhibited extracellular matrix deposition. ALA also decreased hyperglycemia and hyperlipidemia. Activation of the mitochondrial AMPK/PGC1α pathway might be responsible for these ALA-mediated anti-fibrotic effects. Exogenous ALA blocked oxidative stress by activating NRF2. Taken together, these findings demonstrate that exogenous ALA effectively prevents the progression of silicosis in a murine model, likely by stimulating mitochondrial biogenesis and endogenous antioxidant responses. Therefore, ALA can potentially delay the progression of silica-induced pulmonary fibrosis.

Oxidative stress is proposed to be involved in nonalcoholic fatty liver disease (NAFLD). However, antioxidant therapy results in controversial outcomes. Therefore, we generated a new antioxidant/NAFLD mouse model, LiasHigh/HighLeprdb/db mice, by crossbreeding Leprdb/db mice, an obesity mouse model, with LiasHigh/High mice, generated by overexpression of lipoic acid synthase gene (Lias) and having increased endogenous antioxidant capacity, to investigate whether the new model could block the development of NAFLD. We have systemically characterized the novel model based on the main features of human NAFLD, determined the impact of enhanced endogenous antioxidant capacity on the retardation of NAFLD and elucidated the underlying mechanisms using various biological and pathological methods. We found that LiasHigh/HighLeprdb/db mice ameliorated many pathological changes of NAFLD compared with the control. In particular, LiasHigh/HighLeprdb/db mice displayed the improved liver mitochondrial function, reflecting the decline of mitochondrial microvesicular steatosis, and reduced oxidative stress, which mainly contributes to the alleviation of pathologic alterations of the NAFLD progression. Our new model shows that mitochondrial dysfunction is a major pathogenesis for liver steatosis. Overexpression of Lias gene effectively reduces oxidative stress and protects mitochondria, and consequently attenuates NAFLD/NASH.

Both mitoxantrone (MTX) and proteasome inhibitors efficiently trigger immunogenic cell death (ICD) in cancer cells. However, whether the combination of MTX and proteasome inhibitors can synergistically enhance ICD remains unknown. In this study, we showed that the proteasome inhibitors bortezomib (BZM) and carbobenzoxy-L-leucyl-L-leucyl-L-leucinal (MG132) impaired MTX-induced ICD in prostate cancer cells, as measured using ICD biomarkers and dendritic cell activation in vitro. Mice vaccinated with RM-1 mouse prostate cancer cell line treated with BZM or MG132 in combination with MTX showed enhanced tumor growth, and shortened tumor-free, and worse overall survival compared with those treated with MTX alone. In conclusion, we demonstrated that proteasome inhibitors (BZM or MG132) attenuated MTX-induced ICD, suggesting that proteasome activation was required for MTX-induced ICD.

The objective of this study was to evaluate the histopathological effect of gas explosion on rats, and to explore the metabolic alterations associated with gas explosion-induced acute blast lung injury (ABLI) in real roadway environment using metabolomics analyses. All rats were exposed to the gas explosion source at different distance points (160 m and 240 m) except the control group. Respiratory function indexes were monitored and lung tissue analysis was performed to correlate histopathological effect to serum metabolomics. Their sera samples were collected to measure the metabolic alterations by ultra-performance liquid chromatography-mass spectrometry (UPLC-MS). HE staining in lung showed that the gas explosion caused obvious inflammatory pulmonary injury, which was consistent with respiratory function monitoring results and the serum metabolomics analysis results. The metabolomics identified 9 significantly metabolites different between the control- and ABLI rats. 2-aminoadipic acid, L-methionine, L-alanine, L-lysine, L-threonine, cholic acid and L-histidine were significantly increased in the exposed groups. Citric acid and aconitic acid were significantly decreased after exposure. Pathway analyses identified 8 perturbed metabolic pathways, which provided novel potential mechanisms for the gas explosion-induced ABLI. Therefore, metabolomics analysis identified both known and unknown alterations in circulating biomarkers, adding an integral mechanistic insight into the gas explosion-induced ABLI in real roadway environment.

Herein, we report cost effective and body compatible CuS nanoparticles (NPs) derived from a single source precursor as photothermal agent for healing deep cancer and photocatalytic remediation of organic carcinogens. These NPs efficiently kill MCF7 cells (both in vivo and in vitro) under NIR irradiation by raising the temperature of tumor cells. Such materials can be used for the treatment of deep cancer as they can produce a heating effect using high wavelength and deeply penetrating NIR radiation. Furthermore, CuS NPs under solar light irradiation efficiently convert p-nitrophenol (PNP), an environmental carcinogen, to p-aminophenol (PAP) of pharmaceutical implication. In a nutshell, CuS can be used for the treatment of deep cancer and for the remediation of carcinogenic pollutants. There seems an intrinsic connection between the two functions of CuS NPs that need to be explored in length.

Polyguanylic acid potassium salt (PolyG) has an anti-fibrotic G-quadruplex (G4) structure. It could inhibit the expression of nucleolin, a protein involved in cell proliferation and apoptosis. However, its role in regulating nucleolin in silicosis is still unknown. After instillation of 50 μl of crystalline silica suspension (50 mg/ml) into the trachea of C57BL/6 mice, we show that nucleolin expression is upregulated in mouse pulmonary tissue following the treatment with silica and that PolyG, which were injected 2.5 mg/kg body weight into mice by abdomen, could alleviate pulmonary fibrosis through inhibiting the expression of nucleolin. Further, we demonstrated that the expression of the DNA double-strand break (DSB) marker, γ-H2AX, increased in response to silica treatment. PolyG could efficiently reduce the protein expression of γ-H2AX and decreased the level of fibrosis-related genes, such as Col1a1 and Col3a1, as well as the levels of fibrosis-associated proteins α-SMA and vimentin in the lungs of silica-treated mice. These findings show that PolyG could regulate nucleolin and DNA damage repair to control fibrotic response in experimental silicosis and provide a new target for preventive intervention.

In this study, micro/nanoscale LiFePO4/graphene composites are synthesized successfully using a one-step microwave heating method. One-step microwave heating can simplify the reduction step of graphene oxide and provide a convenient, economical, and effective method of preparing graphene composites. The structural analysis shows that LiFePO4/graphene has high phase purity and crystallinity. The morphological analysis shows that LiFePO4/graphene microspheres and micron blocks are composed of densely aggregated nanoparticles; the nanoparticle size can shorten the diffusion path of lithium ions and thus increase the lithium-ion diffusion rate. Additionally, the graphene sheets can provide a rapid transport path for electrons, thus increasing the electronic conductivity of the material. Furthermore, the nanoparticles being packed into the micron graphene sheets can ensure stability in the electrolyte during charging and discharging. Raman analysis reveals that the graphene has a high degree of graphitization. Electrochemical analysis shows that the LiFePO4/graphene has an excellent capacity, high rate performance, and cycle stability. The discharge capacities are 166.3, 156.1, 143.0, 132.4, and 120.9 mAh g−1 at rates of 0.1, 1, 3, 5, and 10 C, respectively. The superior electrochemical performance can be ascribed to the synergy of the shorter lithium-ion diffusion path achieved by LiFePO4 nanoparticles and the conductive networks of graphene.

The removal of residual organics from manganese (Mn) electrochemical solution using combined Fenton oxidation process with adsorption over activated carbon (AC) was investigated. The effect of operating conditions such as dosage of H2O2, H2O2/Fe2+ ratio, initial pH value, reaction temperature, and reaction time on Fenton oxidation was studied. Experimental results indicated that a maximum chemical oxygen demand (COD) of 83.2% was obtained under the optimized set of conditions: H2O2 concentration of 0.15 mol/L, H2O2/Fe2+ molar ratio of 3, initial pH value of 3, reaction temperature of 50 °C, and reaction time of 90 min. The leaching solution was furthered treated over AC and COD removal rate increased to 93.1% under 3.75 g/L dosage of AC, adsorption temperature of 70 °C, and adsorption time of 120 min. The adsorption mechanism of Mn over AC was detailly investigated, while the porous texture of AC was studied by nitrogen adsorption isotherm.

Benzene is a global pollutant and has been established to cause leukemia. To better understand the role of DNA methylation in benzene toxicity, peripheral blood mononuclear cells were collected from six benzene-poisoning patients and six matched controls for genome-wide DNA methylation screening by Illumina Infinium Methylation 450 BeadChip. The Gene Chip Human Gene 2.0 ST Array (Affymetrix) was used to analyze global mRNA expression. Compared with the corresponding sites of controls, 442 sites in patients were hypermethylated, corresponding to 253 genes, and 237 sites were hypomethylated, corresponding to 130 genes. The promoter methylation and mRNA expression of CSF3R, CREB5, and F2R were selected for verification by bisulfite sequencing and real-time PCR in a larger data set with 21 cases and 23 controls. The results indicated that promoter methylation of CSF3R (p = .005) and F2R (p = .015) was significantly higher in cases than in controls. Correlation analysis showed that the promoter methylation of CSF3R (p < .001) and F2R (p < .001) was highly correlated with its mRNA expression. In the poisoning cases, neutrophil percentage was significantly different among the high, middle, and low CSF3R-methylation groups (p = .002). In particular, the neutrophil percentage in the high CSF3R-methylation group (48.10 ± 9.63%) was significantly lower than that in the low CSF3R-methylation group (59.30 ± 6.26%) (p = .012). The correlation coefficient between promoter methylation in CSF3R and the neutrophil percentage was -0.445 (p = .020) in cases and - 0.398 (p = .060) in controls. These results imply that hypermethylation occurs in the CSF3R promoter due to benzene exposure and is significantly associated with a reduction in neutrophils.

Fermentable sugars are valuable intermediates that can be produced from lignocellulosic biomass, in which hemicellulose and cellulose are favorable candidates for their production. In this chapter, the adaptability of a comprehensive strategy for lignocellulose saccharification is presented. Hemicellulose of reed pole can be hydrolyzed for xylose production by dilute acid first, and then the retained residue from acid hydrolysis, rich in cellulose, can be pyrolyzed for levoglucosan production. Such a process highlighted in this chapter exhibits several attractive features: (1) hemicellulose can be nearly and completely saccharified, giving a xylose yield as high as 92.2 wt%, (2) due to the alteration of chemical composition and physical structure by dilute acid pretreatment, the levoglucosan yield from acid pretreated biomass can be as high as 45.9 wt% as compared with that of un-pretreated reed pole (4.8 wt%), (3) improvement of levoglucosan formation and the inhibition of acetic acid formation from acid pretreated biomass can improve fermentability of its pyrolysate. Furthermore, it is demonstrated that the effect of demineralization, hydrolysis of hemicellulose and improvement of levoglucosan yield is ordered as HCl > H2SO4 > H3PO4.