In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists ...In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists of the collapsible ~830 L FEP Teflon film main reactor, in which the atmospheric chemical reactions take place and the formation of SOA occurs under the simulated atmospheric conditions, and the diverse on-line gas- and particle-phase instrumentation, such as the proton transfer reaction mass spectrometer, the synchrotron radiation photoionization mass spectrometer, the aerosol laser time-of-flight mass spectrometer, and other traditional commercial instruments. The initial characterization experiments are described, concerning the temperature and ultraviolet light intensity, the reactivity of the pure air, the wall loss rates of gaseous compounds and particulate matter. And the initial evaluation experiments for SOA yields from the ozonolysis of α-pinene and for mass spectra of the products resulting from the photooxidation of OH initiated isoprene are also presented, which indicate the applicability of this facility on the studies of gas-phase chemical mechanisms as well as the formation of SOA expected in the atmosphere.展开更多
Objective: To evaluate the anti-tumor effects of SeO2 and its mechanisms on three human lung cancer cell lines. Methods: Three lung cancer cells A549, GLC-82 and PG were treated with 3-30 μmol/L SeO2. Flow cytometry ...Objective: To evaluate the anti-tumor effects of SeO2 and its mechanisms on three human lung cancer cell lines. Methods: Three lung cancer cells A549, GLC-82 and PG were treated with 3-30 μmol/L SeO2. Flow cytometry was used to detect apoptosis, and analyze the changes of expression of p53 and Bcl-2, as well as ROS and Ca2+ level within cells. Results:SeO2 markedly inhibited cell proliferation and viability, and prompted apoptosis after 48 h treatment. SeO2 at 10 μmol/L induced 47.8% apoptosis in A549 cells, 40.8% in GLC-82 cells, 18.2% in PG cells. SeO2 at 30 μmol/L induced 37.8% apoposis in PG cells,but did not increase apoptotic raes in other two cells. SeO2 could down-regulate the mean fluorescent intensity of Bcl-2 from 65.8 to 9.6 in A549, but not in GLC-82 and in PG cells, up-regulate wild type p53 level in all three cells. SeO2 decreased the ROS and Ca2+ level markedly within three tested cells. Conclusion: SeO2 showed anti-tumor effect via apoptosis pathway in three lung cancer cell lines. The decrease of ROS and Ca2+ level within cells as well as regulation of Bcl-2 and p53 expression may play important roles in above apoptotic procedure.展开更多
Coal and coal-shale both tend to undergo spontaneous combustion under favourable atmospheric conditions. The Wits-Ehac index has been developed in South Africa since the late 1980's to test the spontaneous combust...Coal and coal-shale both tend to undergo spontaneous combustion under favourable atmospheric conditions. The Wits-Ehac index has been developed in South Africa since the late 1980's to test the spontaneous combustion liability of coal. However, in some cases, the Wits-Ehac index fails to produce tangible results when testing coal-shales. To overcome this problem, a new apparatus has been developed to test carbonaceous materials such as coal and coal-shale under chemical reactions with oxygen and an index has been obtained. This index is called the Wits-CT index. The equipment emulates the influence of oxygen adsorption on carbonaceous material for a period of 24 h without a heating system.The Wits-CT index uses the total carbon content of the sample and the temperature variations obtained from the samples during reaction with oxygen to predict the spontaneous combustion liability. Eighteen samples have been analyzed using both indices and the results are in-line. It was found that coals and coal-shales with higher values of the Wits-CT index are more liable to spontaneous combustion.Further research on different coal-shales is underway in order to establish an extensive database for coal and coal-shales, together with known incidences of self-heating.展开更多
Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a...Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a photosystem Ⅱ-integrated hybrid Z-scheme water splitting system,the backward hydrogen oxidation reaction was significantly suppressed by loading a PtCrOx cocatalyst on a ZrO2/TaON photocatalyst.Due to the weak chemisorption and activation of molecular hydrogen on PtCrOx,where Pt is stabilized in the oxidized forms,Pt^Ⅱ and Pt^Ⅳ,hydrogen oxidation is inhibited.However,it is remarkably well-catalyzed by the metallic Pt cocatalyst,thereby rapidly consuming the produced hydrogen.This work describes an approach to inhibit the backward reaction in the photosystem Ⅱ-integrated hybrid Z-scheme water splitting system using Fe(CN)6^3-/Fe(CN)6^4-redox couple as an electron shuttle.展开更多
The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism ...The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H202 and H20, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with -OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Bronsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by BriSnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*c-o orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H202 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O--O group highly electrophilic to attack the C--O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.展开更多
Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30~100 ℃, water and carbon diox...Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30~100 ℃, water and carbon dioxide gas were formed and from about 105~150 ℃, carbon monoxide was produced. Using the DFT B3LYP method with a 6-311G basis set, the reaction system, where spontaneous combustion between coal and oxygen occurs and produces water and monoxide, has been studied, with the geometric configuration for all stagnation points on the potential reaction energy surface optimized. With a frequency analysis and an IRC method, transient formations were tested. Our results indicate that in the reaction of coal oxidization and spontaneous com-bustion producing carbon dioxide and water, oxygen molecules attack carbon atoms of the terminal of the propyl alcohol group on the lateral chain of benzene rings, which causes this propyl alcohol group to produce the acid (-CH2-CH2-COOH) group and water. This acid group continues its break up into carbon dioxide and the (-CH2-CH3) ethyl group. We have come to the conclusion that this water-and-carbon dioxide-production reaction is spontaneous, based on the observation of the energy released by the reaction.展开更多
This study was conducted to verify and discuss the denitrifying dephosphatation under different levels of nitrate concentration and retention time of anoxic/aerobic process in a Sequencing Batch Reactor (SBR). The res...This study was conducted to verify and discuss the denitrifying dephosphatation under different levels of nitrate concentration and retention time of anoxic/aerobic process in a Sequencing Batch Reactor (SBR). The results of tests demonstrated that there were two kinds of phosphorus-accumulating organisms (PAOs) in the biological excess phosphorus removal (BEPR) system. One was non-DNPAOs that could only use oxygen as terminal electron acceptors, the other was denitrifying PAOs (DNPAOs) that could use both nitrate and oxygen as terminal electron acceptors. Phosphorus uptake efficiency could be attained under anoxic period ranging from 28.7%-96.7% in an anaerobic/anoxic/aerobic system. Experimental results showed that nitrate concentration and retention time of anoxic/aerobic process were the key factors affecting the course of denitrifying dephosphatation.展开更多
Purpose: The objective of this study was to investigate the effects of chronic Rhodiola rosea (R. rosea) supplementation on mental and physical performance, as well as hormonal and oxidative stress biomarkers. Meth...Purpose: The objective of this study was to investigate the effects of chronic Rhodiola rosea (R. rosea) supplementation on mental and physical performance, as well as hormonal and oxidative stress biomarkers. Methods: Twenty-six healthy male students received either R. rosea extract (600 mg/day; RR) or placebo (PL) in a randomized double-blind trial. Prior to supplementation (Term I) and following 4 weeks of supplementation (Term II), the students underwent psychomotor tests for simple and choice reaction time, included in the Vienna Test System. Also, the subjects performed VO2peak test. Blood samples were obtained before and after the test to measure the hormonal profile (cortisol, testosterone, and growth hormone), as well as the biomarkers of oxidative stress (lipid hydroperoxides, total antioxidant capacity, and superoxide dismutase) and muscle damage (creatine kinase). Results: R. rosea ingestion shortened reaction time and total response time. Moreover, a greater relative increase in the number of correct responses was observed in RR group as compared to the PL group. No changes in endurance exercise capacity and hormonal profile were observed after R. rosea ingestion. R. rosea ingestion raised plasma total antioxidant capacity. It did not, however, affect other measured parameters. Conclusion: Chronic R. rosea ingestion does not affect physical performance, but can improve the results of some psychomotor tests (simple and choice reaction time) in young, healthy, and physically active men. The improvements in mental performance, however, at least in our study, seem not to be related to changes in cortisol release or antioxidant activity of R. rosea extract. Thus, the specific mechanisms responsible for these effects still need to be elucidated.2018 Published by Elsevier B.V. on behalf of Shanghai University of Sport. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/).展开更多
Heavy metals pose a potential threat to aquatic organisms. In this study, a static-renewal acute toxicity test was conducted to investigate the effects of cadmium on the antioxidant defense systems (both enzymatic an...Heavy metals pose a potential threat to aquatic organisms. In this study, a static-renewal acute toxicity test was conducted to investigate the effects of cadmium on the antioxidant defense systems (both enzymatic and non-enzymatic) and lipid peroxidaton in liver and gill tissues of juvenile GIFT tilapia Oreochromis niloticus. After 8 days of exposure to Cd (0, 0.016, 0.08, 0.4 and 2 mg/L), livers accumulated significantly more Cd than gills. Catalase (CAT), superoxide dismutase (SOD) and glutathione S-transferase (GST) activities were stimulated only at the highest concentration tested (2 mg/L). Glutathione peroxidase (GPx) activity was stimulated in the gill while inhibited in the liver, these alternations in gill and liver showed a strong relationship with Cd levels in these tissues. This may indicate either a tissue-specific response of GPx to Cd or, most probably, a hormetic effect of Cd on GPx. Cd increased GSH levels and decreased the ratio GSSG/GSH in fish livers at 2 mg/L. Cd exposure resulted in an elevated level of MDA in the livers of fish at 2 mg/L, indicating that Cd caused lipid peroxidation. Taken together, the results demonstrated that Cd altered the enzymatic and non-enzymatic defensive systems and caused lipid peroxidation in O. niloticus at relatively high concentrations (compared to environmentally relevant concentrations). In addition, the results implied that O. niloticus could tolerate high level of Cd in sites polluted by Cd.展开更多
Several microorganisms such as bacteria, fungi, Protozoa, Rotifera, cystic amoeba and algae diagnosed in activated sludge aerobic (Rustumiya treatment plant) and anaerobic reactor. Results have shown a reduction in ...Several microorganisms such as bacteria, fungi, Protozoa, Rotifera, cystic amoeba and algae diagnosed in activated sludge aerobic (Rustumiya treatment plant) and anaerobic reactor. Results have shown a reduction in the turbidity rates when using activated sludge at Rustumiya plant of 76.3 to 2.653 NTU in pre-treatment and final tank respectively, also COD (chemical oxygen demand) amount reduced from 427.263 to 82 mg/L respectively, In addition, concentrations of phosphates and nitrates decreased from 12.083 to 8.426 mg/L and 3.59 to 2.43 mg/L respectively, by removing 30.2% and 32.3% respectively of the final tank. The ratio of ammonia removing was 89.6% for ammonia, reducing process from 1358 to 140 mg/L. Furthermore, sulfates concentration decreased from 30.883 to 23.337 mg/L. However, the system in the anaerobic reactor depends on non-aerated activated sludge. Results show turbidity reduced from 12.5 to 2 NTU in pre-treatment and final tank respectively, also the COD mount reduced from 191 to 130 mg/L, the percentage removal of 31.9%. In addition phosphates, nitrates and sulfates concentrations were decreased by using activated sludge from 17.15 to 8.15, 1.2 to 0.1 and 28 to 9.2 mg/L respectively. The ammonia concentration has reduced from 1.2 to 0. i mg/L where at a removal percentage of 90.9%.展开更多
A coupled system consisting of an upflow membrane-less microbial fuel cell (upflow ML-MFC) and a photobioreactor was developed, and its effectiveness for continuous wastewater treatment and electricity production was ...A coupled system consisting of an upflow membrane-less microbial fuel cell (upflow ML-MFC) and a photobioreactor was developed, and its effectiveness for continuous wastewater treatment and electricity production was evaluated. Wastewater was fed to the upflow ML-MFC to remove chemical oxygen demand (COD), phosphorus and nitrogen with simultaneous electricity generation. The effluent from the cathode compartment of the upflow ML-MFC was then continuously fed to an external photobioreactor for removing the remaining phosphorus and nitrogen using microalgae. Alone, the upflow ML-MFC produces a maximum power density of 481 mW/m 3 , and obtains 77.9% COD, 23.5% total phosphorus (TP) and 97.6% NH4+-N removals. When combined with the photobioreactor, the system achieves 99.3% TP and 99.0% NH4+-N total removal. These results show both the effectiveness and the potential application of the coupled system to continuously treat domestic wastewater and simultaneously generate electricity and biomass.展开更多
Green tides have occurred every year from 2007 to 2014 in the Yellow Sea. Ulva prolifera (Mtiller) J. Agardh has been identified as the bloom-forming alga, co-occurring with U. intestinalis. We observed distinct str...Green tides have occurred every year from 2007 to 2014 in the Yellow Sea. Ulva prolifera (Mtiller) J. Agardh has been identified as the bloom-forming alga, co-occurring with U. intestinalis. We observed distinct strategies for both algal species during green tides. U.prolifera exhibited a high abundance initially and then decreased dramatically, while U. intestinalis persisted throughout. The antioxidant system responses of these two macroalgae were compared in the late phase of a green tide (in-situ) and after laboratory acclimation. Lipid peroxidation and antioxidant system responses differed significantly between the two. Malondialdehyde and hydrogen peroxide contents increased significantly in-situ in U. prolifera, but not in U. intestinalis. In U. prolifera, we observed a significant decrease in total antioxidant ability (T-AOC), antioxidant enzymes (SOD and Apx), and non-enzyme antioxidants (GSH and AsA) in-situ. U. intestinalis showed the same pattern of T-AOC and SOD, but its Gpx, Apx, and GSH responses did not differ significantly. The results suggest that U. prolifera was more susceptible than U. intestinalis to the harsh environmental changes during the late phase of a Yellow Sea green tide. The boom and bust strategy exhibited by U. prolifera and the persistence of U. intestinalis can be explained by differences in enzyme activity and antioxidant systems.展开更多
In this paper, sodium cobalt tetracarbonyl (NaCo(CO)4) was synthesized by using sodium dithionite and zinc powder as the reduction system and cobalt hexahydrate acetate as the precursor in the presence of methanol...In this paper, sodium cobalt tetracarbonyl (NaCo(CO)4) was synthesized by using sodium dithionite and zinc powder as the reduction system and cobalt hexahydrate acetate as the precursor in the presence of methanol solvent. Methyl 3-hydroxypropionate was synthesized via hydroesterification of ethylene oxide (EO) catalyzed by NaCo(CO)4. The influencing factors on the reaction results were discussed, including the different ligands, the molar ratio of solvent and ethylene oxide, the reaction temperature, the reaction time, and the reaction pressure. An optimal catalytic system was obtained by using 3-hydroxypyridine as the ligoad under reaction conditions covering a reaction temperature 65 ℃, a reaction time of 7 h, a reaction pressure of 6 MPa, and a methoaol/EO molar ratio of 3:2. Under the optimal conditions, the conversion of ethylene oxide was equal to 97.86%, while the selectivity and yield of methyl 3-hydroxypropionate reached 88.19% and 86.30%, respectively. Finally, the reaction mechanism of hydroesterification of ethylene oxide catalyzed by NaCo(CO)4 was proposed.展开更多
A dual catalytic system, combing visible light photoredox catalysis and iodide catalysis, has been developed for the functionalization of inert C–H bonds. By doing so, radical allylation reactions of N-aryl-tetrahydr...A dual catalytic system, combing visible light photoredox catalysis and iodide catalysis, has been developed for the functionalization of inert C–H bonds. By doing so, radical allylation reactions of N-aryl-tetrahydroisoquinolines(THIQs) were realized under extremely mild conditions, affording a wide variety of allyl-substituted THIQs in up to 78% yields.展开更多
Electrocatalysis is deemed as a promising approach for sustainable energy conversion and chemical production.Although a variety of cathode reactions(e.g.,hydrogen evolution and CO_(2)/N_(2)reduction)produce valuable f...Electrocatalysis is deemed as a promising approach for sustainable energy conversion and chemical production.Although a variety of cathode reactions(e.g.,hydrogen evolution and CO_(2)/N_(2)reduction)produce valuable fuels and chemicals,the extensively studied oxygen evolution reaction(OER)at anode only generates O_(2),which is not a high-value product.Substituting the OER with thermodynamically more favorable biomass derivative oxidation reactions(BDORs)not only enables energy-saving electrocatalysis,but also provides value-added anode products.Recent achievements have demonstrated that non-noble electrocatalysts are promising for BDORs.Herein,we provide a comprehensive review on recent achievements in the field of electrochemical BDORs catalyzed by non-noble catalysts.We start by summarizing the electrocatalytic oxidation of different types of biomass-derived substrates,aiming to show the advantages of the electrocatalytic pathway and to introduce the state-of-the-art non-noble catalysts.The reaction mechanisms of non-noble-material-catalyzed BDORs are then summarized and classified into three types according to the acceptor of hydrogen species during the dehydrogenation of biomass derivatives.Subsequently,discussions are devoted to the strategies for promoting the performances of non-noble electrocatalysts.Finally,we propose our opinions regarding future trends and major challenges in this field.展开更多
Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used...Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used for a more powerful synergistic effect in the bimetal-catalyzed reactions, providing not only milder reaction conditions and higher reactivity but also excellent reaction selectivity. Herein, we give a brief review on the development of Ni-Al bimetallic catalytic system and highlight recent advances in enantioselective Ni-Al bimetallic catalysis for unreactive bond transformation.展开更多
Development of high-voltage electrolytes with non-flammability is significantly important for future energy storage devices.Aqueous electrolytes are inherently non-flammable,easy to handle,and their electrochemical st...Development of high-voltage electrolytes with non-flammability is significantly important for future energy storage devices.Aqueous electrolytes are inherently non-flammable,easy to handle,and their electrochemical stability windows(ESWs)can be considerably expanded by increasing electrolyte concentrations.However,further breakthroughs of their ESWs encounter bottlenecks because of the limited salt solubility,leading to that most of the high-energy anode materials can hardly function reversibly in aqueous electrolytes.Here,by introducing a non-flammable ionic liquid as co-solvent in a lithium salt/water system,we develop a"water in salt/ionic liquid"(WiSIL)electrolyte with extremely low water content.In such WiSIL electrolyte,commercial niobium pentoxide(Nb2O5)material can operate at a low potential(-1.6 V versus Ag/AgCl)and contribute its full capacity.Consequently,the resultant Nb2O5-based aqueous lithium-ion capacitor is able to operate at a high voltage of 2.8 V along with long cycling stability over 3000 cycles,and displays comparable energy and power performance(51.9 Wh kg^-1 at 0.37 kW kg^-1 and 16.4 Wh kg^-1 at 4.9 kW kg^-1)to those using non-aqueous electrolytes but with improved safety performance and manufacturing efficiency.展开更多
基金This work was supported by the Natural Science Foundation of Anhui Province, China (No.1208085MD59), the National Natural Science Foundation of China (No.U1232209, No.41175121, and No.21307137), the Presidential Foundation of Hefei Institutes of Physical Science, Chinese Academy of Sciences, China (No.YZJJ201302), and the Knowledge Innovation Foundation of the Chinese Academy of Sciences (No.KJCX2-YW-N24).
文摘In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists of the collapsible ~830 L FEP Teflon film main reactor, in which the atmospheric chemical reactions take place and the formation of SOA occurs under the simulated atmospheric conditions, and the diverse on-line gas- and particle-phase instrumentation, such as the proton transfer reaction mass spectrometer, the synchrotron radiation photoionization mass spectrometer, the aerosol laser time-of-flight mass spectrometer, and other traditional commercial instruments. The initial characterization experiments are described, concerning the temperature and ultraviolet light intensity, the reactivity of the pure air, the wall loss rates of gaseous compounds and particulate matter. And the initial evaluation experiments for SOA yields from the ozonolysis of α-pinene and for mass spectra of the products resulting from the photooxidation of OH initiated isoprene are also presented, which indicate the applicability of this facility on the studies of gas-phase chemical mechanisms as well as the formation of SOA expected in the atmosphere.
基金This project was partially supported by Science Foundation of Lanzhou Command of PLA(No.YZ-0106).
文摘Objective: To evaluate the anti-tumor effects of SeO2 and its mechanisms on three human lung cancer cell lines. Methods: Three lung cancer cells A549, GLC-82 and PG were treated with 3-30 μmol/L SeO2. Flow cytometry was used to detect apoptosis, and analyze the changes of expression of p53 and Bcl-2, as well as ROS and Ca2+ level within cells. Results:SeO2 markedly inhibited cell proliferation and viability, and prompted apoptosis after 48 h treatment. SeO2 at 10 μmol/L induced 47.8% apoptosis in A549 cells, 40.8% in GLC-82 cells, 18.2% in PG cells. SeO2 at 30 μmol/L induced 37.8% apoposis in PG cells,but did not increase apoptotic raes in other two cells. SeO2 could down-regulate the mean fluorescent intensity of Bcl-2 from 65.8 to 9.6 in A549, but not in GLC-82 and in PG cells, up-regulate wild type p53 level in all three cells. SeO2 decreased the ROS and Ca2+ level markedly within three tested cells. Conclusion: SeO2 showed anti-tumor effect via apoptosis pathway in three lung cancer cell lines. The decrease of ROS and Ca2+ level within cells as well as regulation of Bcl-2 and p53 expression may play important roles in above apoptotic procedure.
基金conducted in the context of coal-shale spontaneous combustion in the eMalahleni coalfields, South Africa was financially sponsored by Coaltech
文摘Coal and coal-shale both tend to undergo spontaneous combustion under favourable atmospheric conditions. The Wits-Ehac index has been developed in South Africa since the late 1980's to test the spontaneous combustion liability of coal. However, in some cases, the Wits-Ehac index fails to produce tangible results when testing coal-shales. To overcome this problem, a new apparatus has been developed to test carbonaceous materials such as coal and coal-shale under chemical reactions with oxygen and an index has been obtained. This index is called the Wits-CT index. The equipment emulates the influence of oxygen adsorption on carbonaceous material for a period of 24 h without a heating system.The Wits-CT index uses the total carbon content of the sample and the temperature variations obtained from the samples during reaction with oxygen to predict the spontaneous combustion liability. Eighteen samples have been analyzed using both indices and the results are in-line. It was found that coals and coal-shales with higher values of the Wits-CT index are more liable to spontaneous combustion.Further research on different coal-shales is underway in order to establish an extensive database for coal and coal-shales, together with known incidences of self-heating.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)the Key Research Program of Frontier Sciences,CAS(QYZDY-SSW-JSC023)+1 种基金the National Natural Science Foundation of China(21603224,31470339)the National Key R&D Program of China(2017YFA0503700)~~
文摘Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a photosystem Ⅱ-integrated hybrid Z-scheme water splitting system,the backward hydrogen oxidation reaction was significantly suppressed by loading a PtCrOx cocatalyst on a ZrO2/TaON photocatalyst.Due to the weak chemisorption and activation of molecular hydrogen on PtCrOx,where Pt is stabilized in the oxidized forms,Pt^Ⅱ and Pt^Ⅳ,hydrogen oxidation is inhibited.However,it is remarkably well-catalyzed by the metallic Pt cocatalyst,thereby rapidly consuming the produced hydrogen.This work describes an approach to inhibit the backward reaction in the photosystem Ⅱ-integrated hybrid Z-scheme water splitting system using Fe(CN)6^3-/Fe(CN)6^4-redox couple as an electron shuttle.
文摘The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H202 and H20, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with -OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Bronsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by BriSnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*c-o orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H202 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O--O group highly electrophilic to attack the C--O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.
基金Financial support for this work, provided by the National Natural Science Foundation of China (No.50834002)the National Eleventh Five-year Plan Science and Technology Key Project (No. 2006BAK03B05), is gratefully acknowledged
文摘Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30~100 ℃, water and carbon dioxide gas were formed and from about 105~150 ℃, carbon monoxide was produced. Using the DFT B3LYP method with a 6-311G basis set, the reaction system, where spontaneous combustion between coal and oxygen occurs and produces water and monoxide, has been studied, with the geometric configuration for all stagnation points on the potential reaction energy surface optimized. With a frequency analysis and an IRC method, transient formations were tested. Our results indicate that in the reaction of coal oxidization and spontaneous com-bustion producing carbon dioxide and water, oxygen molecules attack carbon atoms of the terminal of the propyl alcohol group on the lateral chain of benzene rings, which causes this propyl alcohol group to produce the acid (-CH2-CH2-COOH) group and water. This acid group continues its break up into carbon dioxide and the (-CH2-CH3) ethyl group. We have come to the conclusion that this water-and-carbon dioxide-production reaction is spontaneous, based on the observation of the energy released by the reaction.
基金Sponsored by the National Natural Science Foundation of China(Grant No50008014)
文摘This study was conducted to verify and discuss the denitrifying dephosphatation under different levels of nitrate concentration and retention time of anoxic/aerobic process in a Sequencing Batch Reactor (SBR). The results of tests demonstrated that there were two kinds of phosphorus-accumulating organisms (PAOs) in the biological excess phosphorus removal (BEPR) system. One was non-DNPAOs that could only use oxygen as terminal electron acceptors, the other was denitrifying PAOs (DNPAOs) that could use both nitrate and oxygen as terminal electron acceptors. Phosphorus uptake efficiency could be attained under anoxic period ranging from 28.7%-96.7% in an anaerobic/anoxic/aerobic system. Experimental results showed that nitrate concentration and retention time of anoxic/aerobic process were the key factors affecting the course of denitrifying dephosphatation.
基金financed by the project of Józef Pilsudski University of Physical Education in Warsaw,Faculty of Physical Education and Sport in Biala Podlaska BW/Ⅲ/27
文摘Purpose: The objective of this study was to investigate the effects of chronic Rhodiola rosea (R. rosea) supplementation on mental and physical performance, as well as hormonal and oxidative stress biomarkers. Methods: Twenty-six healthy male students received either R. rosea extract (600 mg/day; RR) or placebo (PL) in a randomized double-blind trial. Prior to supplementation (Term I) and following 4 weeks of supplementation (Term II), the students underwent psychomotor tests for simple and choice reaction time, included in the Vienna Test System. Also, the subjects performed VO2peak test. Blood samples were obtained before and after the test to measure the hormonal profile (cortisol, testosterone, and growth hormone), as well as the biomarkers of oxidative stress (lipid hydroperoxides, total antioxidant capacity, and superoxide dismutase) and muscle damage (creatine kinase). Results: R. rosea ingestion shortened reaction time and total response time. Moreover, a greater relative increase in the number of correct responses was observed in RR group as compared to the PL group. No changes in endurance exercise capacity and hormonal profile were observed after R. rosea ingestion. R. rosea ingestion raised plasma total antioxidant capacity. It did not, however, affect other measured parameters. Conclusion: Chronic R. rosea ingestion does not affect physical performance, but can improve the results of some psychomotor tests (simple and choice reaction time) in young, healthy, and physically active men. The improvements in mental performance, however, at least in our study, seem not to be related to changes in cortisol release or antioxidant activity of R. rosea extract. Thus, the specific mechanisms responsible for these effects still need to be elucidated.2018 Published by Elsevier B.V. on behalf of Shanghai University of Sport. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/).
文摘Heavy metals pose a potential threat to aquatic organisms. In this study, a static-renewal acute toxicity test was conducted to investigate the effects of cadmium on the antioxidant defense systems (both enzymatic and non-enzymatic) and lipid peroxidaton in liver and gill tissues of juvenile GIFT tilapia Oreochromis niloticus. After 8 days of exposure to Cd (0, 0.016, 0.08, 0.4 and 2 mg/L), livers accumulated significantly more Cd than gills. Catalase (CAT), superoxide dismutase (SOD) and glutathione S-transferase (GST) activities were stimulated only at the highest concentration tested (2 mg/L). Glutathione peroxidase (GPx) activity was stimulated in the gill while inhibited in the liver, these alternations in gill and liver showed a strong relationship with Cd levels in these tissues. This may indicate either a tissue-specific response of GPx to Cd or, most probably, a hormetic effect of Cd on GPx. Cd increased GSH levels and decreased the ratio GSSG/GSH in fish livers at 2 mg/L. Cd exposure resulted in an elevated level of MDA in the livers of fish at 2 mg/L, indicating that Cd caused lipid peroxidation. Taken together, the results demonstrated that Cd altered the enzymatic and non-enzymatic defensive systems and caused lipid peroxidation in O. niloticus at relatively high concentrations (compared to environmentally relevant concentrations). In addition, the results implied that O. niloticus could tolerate high level of Cd in sites polluted by Cd.
文摘Several microorganisms such as bacteria, fungi, Protozoa, Rotifera, cystic amoeba and algae diagnosed in activated sludge aerobic (Rustumiya treatment plant) and anaerobic reactor. Results have shown a reduction in the turbidity rates when using activated sludge at Rustumiya plant of 76.3 to 2.653 NTU in pre-treatment and final tank respectively, also COD (chemical oxygen demand) amount reduced from 427.263 to 82 mg/L respectively, In addition, concentrations of phosphates and nitrates decreased from 12.083 to 8.426 mg/L and 3.59 to 2.43 mg/L respectively, by removing 30.2% and 32.3% respectively of the final tank. The ratio of ammonia removing was 89.6% for ammonia, reducing process from 1358 to 140 mg/L. Furthermore, sulfates concentration decreased from 30.883 to 23.337 mg/L. However, the system in the anaerobic reactor depends on non-aerated activated sludge. Results show turbidity reduced from 12.5 to 2 NTU in pre-treatment and final tank respectively, also the COD mount reduced from 191 to 130 mg/L, the percentage removal of 31.9%. In addition phosphates, nitrates and sulfates concentrations were decreased by using activated sludge from 17.15 to 8.15, 1.2 to 0.1 and 28 to 9.2 mg/L respectively. The ammonia concentration has reduced from 1.2 to 0. i mg/L where at a removal percentage of 90.9%.
基金Projects(2009GG10005004, 2010GHY10504) supported by the Scientific and Technological Foundation of Shandong Province,ChinaProject(2011GHY11531) supported by the Science and Technology Development Program of Shandong Province,ChinaProject(ZR2009BM015) supported by the Natural Science Foundation of Shandong Province,China
文摘A coupled system consisting of an upflow membrane-less microbial fuel cell (upflow ML-MFC) and a photobioreactor was developed, and its effectiveness for continuous wastewater treatment and electricity production was evaluated. Wastewater was fed to the upflow ML-MFC to remove chemical oxygen demand (COD), phosphorus and nitrogen with simultaneous electricity generation. The effluent from the cathode compartment of the upflow ML-MFC was then continuously fed to an external photobioreactor for removing the remaining phosphorus and nitrogen using microalgae. Alone, the upflow ML-MFC produces a maximum power density of 481 mW/m 3 , and obtains 77.9% COD, 23.5% total phosphorus (TP) and 97.6% NH4+-N removals. When combined with the photobioreactor, the system achieves 99.3% TP and 99.0% NH4+-N total removal. These results show both the effectiveness and the potential application of the coupled system to continuously treat domestic wastewater and simultaneously generate electricity and biomass.
基金Supported by the China Postdoctoral Science Foundation(No.2013M531648)the Natural Science Foundation of Shandong Province(No.ZR2014DP008)+2 种基金the Fundamental Research Funds for the Central Universities(No.201513046)the National Special Research Fund for Non-Profit Marine Sector(No.201305009)the Joint Funds of the National Natural Science Foundation of China(No.U1406403)
文摘Green tides have occurred every year from 2007 to 2014 in the Yellow Sea. Ulva prolifera (Mtiller) J. Agardh has been identified as the bloom-forming alga, co-occurring with U. intestinalis. We observed distinct strategies for both algal species during green tides. U.prolifera exhibited a high abundance initially and then decreased dramatically, while U. intestinalis persisted throughout. The antioxidant system responses of these two macroalgae were compared in the late phase of a green tide (in-situ) and after laboratory acclimation. Lipid peroxidation and antioxidant system responses differed significantly between the two. Malondialdehyde and hydrogen peroxide contents increased significantly in-situ in U. prolifera, but not in U. intestinalis. In U. prolifera, we observed a significant decrease in total antioxidant ability (T-AOC), antioxidant enzymes (SOD and Apx), and non-enzyme antioxidants (GSH and AsA) in-situ. U. intestinalis showed the same pattern of T-AOC and SOD, but its Gpx, Apx, and GSH responses did not differ significantly. The results suggest that U. prolifera was more susceptible than U. intestinalis to the harsh environmental changes during the late phase of a Yellow Sea green tide. The boom and bust strategy exhibited by U. prolifera and the persistence of U. intestinalis can be explained by differences in enzyme activity and antioxidant systems.
基金supported by the Guangdong Province Natural Science Foundation (No.10152500002000019)the Maoming City Science and Technology Planning Project(No.2014069)
文摘In this paper, sodium cobalt tetracarbonyl (NaCo(CO)4) was synthesized by using sodium dithionite and zinc powder as the reduction system and cobalt hexahydrate acetate as the precursor in the presence of methanol solvent. Methyl 3-hydroxypropionate was synthesized via hydroesterification of ethylene oxide (EO) catalyzed by NaCo(CO)4. The influencing factors on the reaction results were discussed, including the different ligands, the molar ratio of solvent and ethylene oxide, the reaction temperature, the reaction time, and the reaction pressure. An optimal catalytic system was obtained by using 3-hydroxypyridine as the ligoad under reaction conditions covering a reaction temperature 65 ℃, a reaction time of 7 h, a reaction pressure of 6 MPa, and a methoaol/EO molar ratio of 3:2. Under the optimal conditions, the conversion of ethylene oxide was equal to 97.86%, while the selectivity and yield of methyl 3-hydroxypropionate reached 88.19% and 86.30%, respectively. Finally, the reaction mechanism of hydroesterification of ethylene oxide catalyzed by NaCo(CO)4 was proposed.
基金supported by the National Natural Science Foundation of China(2123200321202053+2 种基金21572074)the Foundation for the Author of National Excellent Doctoral Dissertation of China(201422)Outstanding Youth Funding in Hubei Province(2015CFA033)
文摘A dual catalytic system, combing visible light photoredox catalysis and iodide catalysis, has been developed for the functionalization of inert C–H bonds. By doing so, radical allylation reactions of N-aryl-tetrahydroisoquinolines(THIQs) were realized under extremely mild conditions, affording a wide variety of allyl-substituted THIQs in up to 78% yields.
基金supported by the National Natural Science Foundation of China (21978147 and 21935001)Haihe Laboratory of Sustainable Chemical Transformationssupported by the Shuimu Tsinghua Scholar Program (2021SM072)
文摘Electrocatalysis is deemed as a promising approach for sustainable energy conversion and chemical production.Although a variety of cathode reactions(e.g.,hydrogen evolution and CO_(2)/N_(2)reduction)produce valuable fuels and chemicals,the extensively studied oxygen evolution reaction(OER)at anode only generates O_(2),which is not a high-value product.Substituting the OER with thermodynamically more favorable biomass derivative oxidation reactions(BDORs)not only enables energy-saving electrocatalysis,but also provides value-added anode products.Recent achievements have demonstrated that non-noble electrocatalysts are promising for BDORs.Herein,we provide a comprehensive review on recent achievements in the field of electrochemical BDORs catalyzed by non-noble catalysts.We start by summarizing the electrocatalytic oxidation of different types of biomass-derived substrates,aiming to show the advantages of the electrocatalytic pathway and to introduce the state-of-the-art non-noble catalysts.The reaction mechanisms of non-noble-material-catalyzed BDORs are then summarized and classified into three types according to the acceptor of hydrogen species during the dehydrogenation of biomass derivatives.Subsequently,discussions are devoted to the strategies for promoting the performances of non-noble electrocatalysts.Finally,we propose our opinions regarding future trends and major challenges in this field.
基金supported by the National Natural Science Foundation of China (21672107)the “1000-Youth Talents Plan”
文摘Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used for a more powerful synergistic effect in the bimetal-catalyzed reactions, providing not only milder reaction conditions and higher reactivity but also excellent reaction selectivity. Herein, we give a brief review on the development of Ni-Al bimetallic catalytic system and highlight recent advances in enantioselective Ni-Al bimetallic catalysis for unreactive bond transformation.
基金supported by the National Natural Science Foundations of China(21573265 and 21673263)the Zhaoqing Municipal Science and Technology Bureau(2019K038)+2 种基金the Key Cultivation Projects of the Institute in 13th Five-Yearthe Instruments Function Development&Technology Innovation Project of Chinese Academy of Sciences(2020g105)the Western Young Scholars Foundations of Chinese Academy of Sciences。
文摘Development of high-voltage electrolytes with non-flammability is significantly important for future energy storage devices.Aqueous electrolytes are inherently non-flammable,easy to handle,and their electrochemical stability windows(ESWs)can be considerably expanded by increasing electrolyte concentrations.However,further breakthroughs of their ESWs encounter bottlenecks because of the limited salt solubility,leading to that most of the high-energy anode materials can hardly function reversibly in aqueous electrolytes.Here,by introducing a non-flammable ionic liquid as co-solvent in a lithium salt/water system,we develop a"water in salt/ionic liquid"(WiSIL)electrolyte with extremely low water content.In such WiSIL electrolyte,commercial niobium pentoxide(Nb2O5)material can operate at a low potential(-1.6 V versus Ag/AgCl)and contribute its full capacity.Consequently,the resultant Nb2O5-based aqueous lithium-ion capacitor is able to operate at a high voltage of 2.8 V along with long cycling stability over 3000 cycles,and displays comparable energy and power performance(51.9 Wh kg^-1 at 0.37 kW kg^-1 and 16.4 Wh kg^-1 at 4.9 kW kg^-1)to those using non-aqueous electrolytes but with improved safety performance and manufacturing efficiency.