Pyrolusite reduction processes by three major biomass components cellulose,hemicelluloses and lignin,represented by CP,HP and LP,respectively,were investigated by thermogravimetric analyzer coupled with Fourier transf...Pyrolusite reduction processes by three major biomass components cellulose,hemicelluloses and lignin,represented by CP,HP and LP,respectively,were investigated by thermogravimetric analyzer coupled with Fourier transform infrared spectrometry(TG-FTIR).The Sestak-Berggren(SB) equation was used to evaluate the kinetics of reduction processes.TG analysis reveals that the main reduction processes occur at 250-410 ℃,220-390 ℃,and 190-410 ℃ for CP,HP,and LP,respectively.FT-IR and XRD results indicate that various reducing volatiles(e.g.aldehydes,furans,ketones and alcohols) are produced from the pyrolysis with the three major components,which directly reduce MnO_2 in ore to MnO.The processes are described by the SB equation with three parameters(m,n,p).Their non-zero values suggest that pyrolusite reduction is controlled by the diffusion of reducing gaseous products through an ash/inert layer associated with minerals.The apparent activation energies for pyrolusite reduction by CP,HP and LP are 40.48,25.70 and 40.10 kJ·mol^(-1),respectively.展开更多
To solve the increasing model complexity due to several input variables and large correlations under variable load conditions,a dynamic modeling method combining a kernel extreme learning machine(KELM)and principal co...To solve the increasing model complexity due to several input variables and large correlations under variable load conditions,a dynamic modeling method combining a kernel extreme learning machine(KELM)and principal component analysis(PCA)was proposed and applied to the prediction of nitrogen oxide(NO_(x))concentration at the outlet of a selective catalytic reduction(SCR)denitrification system.First,PCA is applied to the feature information extraction of input data,and the current and previous sequence values of the extracted information are used as the inputs of the KELM model to reflect the dynamic characteristics of the NO_(x)concentration at the SCR outlet.Then,the model takes the historical data of the NO_(x)concentration at the SCR outlet as the model input to improve its accuracy.Finally,an optimization algorithm is used to determine the optimal parameters of the model.Compared with the Gaussian process regression,long short-term memory,and convolutional neural network models,the prediction errors are reduced by approximately 78.4%,67.6%,and 59.3%,respectively.The results indicate that the proposed dynamic model structure is reliable and can accurately predict NO_(x)concentrations at the outlet of the SCR system.展开更多
In the present study, we aimed to intensively study the chemical constituents, especially organic acids from a medicinal plant Portulaca oleracea L., and screen their anti-inflammatory and quinone reductase (QR, a ph...In the present study, we aimed to intensively study the chemical constituents, especially organic acids from a medicinal plant Portulaca oleracea L., and screen their anti-inflammatory and quinone reductase (QR, a phase II detoxyfication enzyme) inductive activity. A total of 20 compounds were isolated and identified based on spectroscopic methods, as succinic acid (1), mono-methyl succinate (2), L-malic acid (3), L-l-methyl malate (4), L-4-methyl malate (5), L-dimethyl malate (6), L-6-ethyl citrate (7), L-1-methyl citrate (8), L-1,5-dimethyl citrate (9), 4-hydroxy-5-methylfuran-3-carboxylic acid (10), 5-hydroxymethyl-furoic acid (11), stearic acid (12), L-pyroglutamic acid (13), cyclo-(tyrosine-leucine) (14), L-isoleucine (15), (-)-dehydrovomifoliol (16), (-)-epiloliolide (17), 3,4-dihydroxyphenylethanol (18), succinimide (19), and uracil (20). Among them, 14 compounds (2, 4-8, 10, 11, 13-18) were isolated from P. oleracea for the first time. Compotmd 18 (12.5 μM) exhibited potent anti-inflammatory effect in lipopolysaccharide (LPS)-induced macrophage cells (RAW264.7) by reducing NO production, and it also increased QR activity in Hepa lclc7 cells. Compound 16 (50 μM) showed weak QR inductive activity. None of other compounds showed anti-inflammatory or QR inductive activities.展开更多
Iron and manganese oxides are common components of soils. They frequently occur in nodules constituting important soil sorbents and play a crucial role in a number of chemical reactions in the soil environment. In add...Iron and manganese oxides are common components of soils. They frequently occur in nodules constituting important soil sorbents and play a crucial role in a number of chemical reactions in the soil environment. In addition, the oxides are very sensitive to environmental changes (moisture, pH, Eh) constituting important indicators of soil-forming processes and water movement in the landscape. The objectives of the study were: i) to examine the distribution and size of Fe-Mn nodules in Albeluvisols containing a fragipan horizon; ii) to determine the morphology and chemical composition of the nodules, and iii) to estimate the effect of the fragipan horizon on water movement within the soil profile. An investigation was carried out on five soil profiles containing a fragipan horizon and classified as Fragic Albeluvisols within the Carpathian Foothills in Poland. In the Albeluvisols studied, the maximum concentration of Fe-Mn nodules occurred in the horizon lying directly on the fragipan horizon. This suggests that the pan acts as a natural barrier restricting water infiltration and leads to the seasonal development of a perched water table promoting redox processes. The most common are coarse (1-0.5 mm) and medium (0.5-0.25 mm) irregular Fe-Mn nodules showing a gradual boundary and undifferentiated internal fabric. Eluvial horizons contained also larger amounts of round and dense nodules with a sharp boundary, suggesting frequent oxidation and reduction. The fragipan horizon contained mainly irregular and soft nodules, suggesting longer saturation with water during the year. Concentrations of trace elements (Cu, Zn) and P were higher within Fe-Mn nodules than in the surrounding soil materials, showing that iron and manganese oxides adsorbed and immobilised these elements.展开更多
In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. Th...In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. This iron deposit is coherent with the sedimentary rock succession of the Yuanjiacun Formation in the lower Lliliang Group, and was interpreted to be deposited at 2.3-2.1 Ga, based on ages of overlying and underlying volcanic strata. This age overlaps with the time range of the Great Oxidation Event (GOE, 2.4-2.2 Ga). The Yuanjiacun BIF consists mainly of subhedral-xenomorphic magnetite and quartz and rarely other minerals with a lower degree of metamorphism, from greenschist to lower amphibolite facies. The geochemical characteristics of this BIF are similar to those of Superior-type BIFs. Prominent positive La, Y, and Eu anomalies normalized by the Post Archean Australian Shale (PAAS) indicate that the primary chemical precipitate is a result of solutions that repre- sent mixtures of seawater and high-T hydrothermal fluids. The contamination from crustal detritus found is negligible based on low abundances of Al2O3 and TiO2 (〈0.5%) and of trace elements such as Th, Hf, Zr, and Sc (〈1.5 ppm), as well as the lack of co-variations between Al2O3 and TiO2. In particular, the Yuanjiacun BIF samples do not display significant negative Ce anom- alies like those of the Archean iron formations, but rather, the Yuanjiacun BIF samples exhibit prominent positive Ce anoma- lies, low Y/Ho ratios, and high light to heavy REE ((Pr/Yb)sN) ratios, which are essentially consistent with the late Paleoprote- rozoic (〈2.0 Ga) BIFs around the world. These characteristics of the Yuanjiacun BIF samples imply that the ancient ocean (2.3-2.1 Ga) was redox-stratified from oxic shallow water to deeper anoxic water. The specific redox conditions of the ancient ocean may be related to the GOE, which gave rise to the oxidation of Ce and Mn in the upper water, and to the presence of a Mn oxide shuttle in the ocean, resulting in varying REE patterns due to the precipitation and dissolution of this Mn oxide shut tle under different redox states. Therefore, the Yuanjiacun BIF appears to have formed near the redoxcline and lower-level reduced marine water.展开更多
The mordenite(MOR) nanoparticles(MNPs)with ultra-small crystallites(~30 nm) were synthesized by using tetraethylammonium bromide(TEAB) as structure directing agent at low temperature(403K). The formation of ...The mordenite(MOR) nanoparticles(MNPs)with ultra-small crystallites(~30 nm) were synthesized by using tetraethylammonium bromide(TEAB) as structure directing agent at low temperature(403K). The formation of MNPs was considered to be due to high concentration of TEAB and occurrence of limiting Ostwald ripening at low temperature. The MNPs exhibited not only higher catalytic activity at low temperature for selective catalytic reduction of NOx but also higher catalytic activity and longer lifetime for disproportionation of toluene than conventional MOR(cMOR) bulk crystals.展开更多
A novel tandem reductive amination/intermolecular nucleophilic aromatic substitution (SNAr) sequence has been established for the synthesis of amine containing pyrimidine in formation of one carbon-oxygen and one carb...A novel tandem reductive amination/intermolecular nucleophilic aromatic substitution (SNAr) sequence has been established for the synthesis of amine containing pyrimidine in formation of one carbon-oxygen and one carbon-nitrogen bonds in a one-pot fashion. Treatment of aldehyde with arylamine, 2-methanesulfonyl-4,6-dimeth-oxypyrimidine and sodium borohydride provides good overall yield. The p-toluenesulfonic acid (PTSA) can be used as activator and is generally needed in the reaction. Dioxane is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF), MeCN, toluene and dichloromethane. The procedure is carried out effectively in the presence of K2CO3. The reaction proceeds smoothly with aromatic aldehydes and arylamines possessing elec-tron-donating or-withdrawing groups. This method can be applied to the synthesis of the oilseed rape herbicide and is superior to the classical one in several aspects: cutting out several purification steps, minimizing solvent use and chemical waste, and saving time. Its advantages such as operational convenience, high-efficient synthesis, and starting material availability make it a desirable method for preparing amines with molecular diversity and biological activity.展开更多
A novel and facile seed-mediated method for the preparation of monodispersed gold nanorods(GNRs) is presented by introducing pyrogallol as a reductant. Fast Fourier transformation of high-resolution transmission elect...A novel and facile seed-mediated method for the preparation of monodispersed gold nanorods(GNRs) is presented by introducing pyrogallol as a reductant. Fast Fourier transformation of high-resolution transmission electron microscopy reveals that the synthesized GNRs are single crystalline. The longitudinal surface plasmon resonance of GNRs can be finely tuned by varying silver ion concentrations or seed amounts. Also, both thick(diameter >30 nm) and thin(diameter <10 nm) GNRs with exceptional monodispersity can be well prepared by this method. These findings indicate that this method has a greater performance in controlling the morphology of GNRs than that of traditional approach with ascorbic acid as a reductant.展开更多
基金Supported by the National Natural Science Foundation of China(21166003)the Doctoral Foundation of Ministry of Education of China(20114501110004)
文摘Pyrolusite reduction processes by three major biomass components cellulose,hemicelluloses and lignin,represented by CP,HP and LP,respectively,were investigated by thermogravimetric analyzer coupled with Fourier transform infrared spectrometry(TG-FTIR).The Sestak-Berggren(SB) equation was used to evaluate the kinetics of reduction processes.TG analysis reveals that the main reduction processes occur at 250-410 ℃,220-390 ℃,and 190-410 ℃ for CP,HP,and LP,respectively.FT-IR and XRD results indicate that various reducing volatiles(e.g.aldehydes,furans,ketones and alcohols) are produced from the pyrolysis with the three major components,which directly reduce MnO_2 in ore to MnO.The processes are described by the SB equation with three parameters(m,n,p).Their non-zero values suggest that pyrolusite reduction is controlled by the diffusion of reducing gaseous products through an ash/inert layer associated with minerals.The apparent activation energies for pyrolusite reduction by CP,HP and LP are 40.48,25.70 and 40.10 kJ·mol^(-1),respectively.
基金The National Natural Science Foundation of China(No.71471060)the Natural Science Foundation of Hebei Province(No.E2018502111)。
文摘To solve the increasing model complexity due to several input variables and large correlations under variable load conditions,a dynamic modeling method combining a kernel extreme learning machine(KELM)and principal component analysis(PCA)was proposed and applied to the prediction of nitrogen oxide(NO_(x))concentration at the outlet of a selective catalytic reduction(SCR)denitrification system.First,PCA is applied to the feature information extraction of input data,and the current and previous sequence values of the extracted information are used as the inputs of the KELM model to reflect the dynamic characteristics of the NO_(x)concentration at the SCR outlet.Then,the model takes the historical data of the NO_(x)concentration at the SCR outlet as the model input to improve its accuracy.Finally,an optimization algorithm is used to determine the optimal parameters of the model.Compared with the Gaussian process regression,long short-term memory,and convolutional neural network models,the prediction errors are reduced by approximately 78.4%,67.6%,and 59.3%,respectively.The results indicate that the proposed dynamic model structure is reliable and can accurately predict NO_(x)concentrations at the outlet of the SCR system.
基金National Natural Science Foundation of China(Grant No.81073005)Science and Technology Development Program of Shandong Province(Grant No.2014GSF119007)+2 种基金Major Project of Science and Technology of Shandong Province(Grant No.2015ZDJS04001)Young Scholars Program of Shandong University(Grant No.YSPSDU2015WLJH50)China-Australia Centre for Health Sciences Research(2015)
文摘In the present study, we aimed to intensively study the chemical constituents, especially organic acids from a medicinal plant Portulaca oleracea L., and screen their anti-inflammatory and quinone reductase (QR, a phase II detoxyfication enzyme) inductive activity. A total of 20 compounds were isolated and identified based on spectroscopic methods, as succinic acid (1), mono-methyl succinate (2), L-malic acid (3), L-l-methyl malate (4), L-4-methyl malate (5), L-dimethyl malate (6), L-6-ethyl citrate (7), L-1-methyl citrate (8), L-1,5-dimethyl citrate (9), 4-hydroxy-5-methylfuran-3-carboxylic acid (10), 5-hydroxymethyl-furoic acid (11), stearic acid (12), L-pyroglutamic acid (13), cyclo-(tyrosine-leucine) (14), L-isoleucine (15), (-)-dehydrovomifoliol (16), (-)-epiloliolide (17), 3,4-dihydroxyphenylethanol (18), succinimide (19), and uracil (20). Among them, 14 compounds (2, 4-8, 10, 11, 13-18) were isolated from P. oleracea for the first time. Compotmd 18 (12.5 μM) exhibited potent anti-inflammatory effect in lipopolysaccharide (LPS)-induced macrophage cells (RAW264.7) by reducing NO production, and it also increased QR activity in Hepa lclc7 cells. Compound 16 (50 μM) showed weak QR inductive activity. None of other compounds showed anti-inflammatory or QR inductive activities.
基金Supported by the Polish State Committee for Scientific Research (No. N N305 120934)
文摘Iron and manganese oxides are common components of soils. They frequently occur in nodules constituting important soil sorbents and play a crucial role in a number of chemical reactions in the soil environment. In addition, the oxides are very sensitive to environmental changes (moisture, pH, Eh) constituting important indicators of soil-forming processes and water movement in the landscape. The objectives of the study were: i) to examine the distribution and size of Fe-Mn nodules in Albeluvisols containing a fragipan horizon; ii) to determine the morphology and chemical composition of the nodules, and iii) to estimate the effect of the fragipan horizon on water movement within the soil profile. An investigation was carried out on five soil profiles containing a fragipan horizon and classified as Fragic Albeluvisols within the Carpathian Foothills in Poland. In the Albeluvisols studied, the maximum concentration of Fe-Mn nodules occurred in the horizon lying directly on the fragipan horizon. This suggests that the pan acts as a natural barrier restricting water infiltration and leads to the seasonal development of a perched water table promoting redox processes. The most common are coarse (1-0.5 mm) and medium (0.5-0.25 mm) irregular Fe-Mn nodules showing a gradual boundary and undifferentiated internal fabric. Eluvial horizons contained also larger amounts of round and dense nodules with a sharp boundary, suggesting frequent oxidation and reduction. The fragipan horizon contained mainly irregular and soft nodules, suggesting longer saturation with water during the year. Concentrations of trace elements (Cu, Zn) and P were higher within Fe-Mn nodules than in the surrounding soil materials, showing that iron and manganese oxides adsorbed and immobilised these elements.
基金supported by the Major State Basic Research Programme of the People’s Republic of China(Grant No.2012CB416601)the Knowledge Innovation Programme of the Chinese Academy of Sciences(Grant No.KZCX2-YW-Q04-07)
文摘In China, most Precambrian banded iron formations (BIFs) are situated in the North China Craton. The Yuanjiacun iron depos- it, located in the Ltlliang area, is arguably the most representative Superior-type BIF. This iron deposit is coherent with the sedimentary rock succession of the Yuanjiacun Formation in the lower Lliliang Group, and was interpreted to be deposited at 2.3-2.1 Ga, based on ages of overlying and underlying volcanic strata. This age overlaps with the time range of the Great Oxidation Event (GOE, 2.4-2.2 Ga). The Yuanjiacun BIF consists mainly of subhedral-xenomorphic magnetite and quartz and rarely other minerals with a lower degree of metamorphism, from greenschist to lower amphibolite facies. The geochemical characteristics of this BIF are similar to those of Superior-type BIFs. Prominent positive La, Y, and Eu anomalies normalized by the Post Archean Australian Shale (PAAS) indicate that the primary chemical precipitate is a result of solutions that repre- sent mixtures of seawater and high-T hydrothermal fluids. The contamination from crustal detritus found is negligible based on low abundances of Al2O3 and TiO2 (〈0.5%) and of trace elements such as Th, Hf, Zr, and Sc (〈1.5 ppm), as well as the lack of co-variations between Al2O3 and TiO2. In particular, the Yuanjiacun BIF samples do not display significant negative Ce anom- alies like those of the Archean iron formations, but rather, the Yuanjiacun BIF samples exhibit prominent positive Ce anoma- lies, low Y/Ho ratios, and high light to heavy REE ((Pr/Yb)sN) ratios, which are essentially consistent with the late Paleoprote- rozoic (〈2.0 Ga) BIFs around the world. These characteristics of the Yuanjiacun BIF samples imply that the ancient ocean (2.3-2.1 Ga) was redox-stratified from oxic shallow water to deeper anoxic water. The specific redox conditions of the ancient ocean may be related to the GOE, which gave rise to the oxidation of Ce and Mn in the upper water, and to the presence of a Mn oxide shuttle in the ocean, resulting in varying REE patterns due to the precipitation and dissolution of this Mn oxide shut tle under different redox states. Therefore, the Yuanjiacun BIF appears to have formed near the redoxcline and lower-level reduced marine water.
基金supported by the National Natural Science Foundation of China (21533002 and 21571128)the National Excellent Doctoral Dissertation of China (201454)the National Key R&D Program of China (2016YFC0205900)
文摘The mordenite(MOR) nanoparticles(MNPs)with ultra-small crystallites(~30 nm) were synthesized by using tetraethylammonium bromide(TEAB) as structure directing agent at low temperature(403K). The formation of MNPs was considered to be due to high concentration of TEAB and occurrence of limiting Ostwald ripening at low temperature. The MNPs exhibited not only higher catalytic activity at low temperature for selective catalytic reduction of NOx but also higher catalytic activity and longer lifetime for disproportionation of toluene than conventional MOR(cMOR) bulk crystals.
基金Project (Nos. Y407118 and D3080282) supported by the Natural Science Foundation of Zhejiang Province, China
文摘A novel tandem reductive amination/intermolecular nucleophilic aromatic substitution (SNAr) sequence has been established for the synthesis of amine containing pyrimidine in formation of one carbon-oxygen and one carbon-nitrogen bonds in a one-pot fashion. Treatment of aldehyde with arylamine, 2-methanesulfonyl-4,6-dimeth-oxypyrimidine and sodium borohydride provides good overall yield. The p-toluenesulfonic acid (PTSA) can be used as activator and is generally needed in the reaction. Dioxane is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF), MeCN, toluene and dichloromethane. The procedure is carried out effectively in the presence of K2CO3. The reaction proceeds smoothly with aromatic aldehydes and arylamines possessing elec-tron-donating or-withdrawing groups. This method can be applied to the synthesis of the oilseed rape herbicide and is superior to the classical one in several aspects: cutting out several purification steps, minimizing solvent use and chemical waste, and saving time. Its advantages such as operational convenience, high-efficient synthesis, and starting material availability make it a desirable method for preparing amines with molecular diversity and biological activity.
基金supported by the National Natural Science Foundation of China(61271056,61301039,61102031,21205036)Hunan Provincial Natural Science Foundation of China(13JJ4091,12JJ6060)+2 种基金China Postdoctoral Science Foundation funded projects(2014M550261,2014T70459)the Scientific Research Fund of Hunan Provincial Education Department(13A003)the Economical Forest Cultivation and Utilization of 2011 Collaborative Innovation Center in Hunan Province[(2013)448]
文摘A novel and facile seed-mediated method for the preparation of monodispersed gold nanorods(GNRs) is presented by introducing pyrogallol as a reductant. Fast Fourier transformation of high-resolution transmission electron microscopy reveals that the synthesized GNRs are single crystalline. The longitudinal surface plasmon resonance of GNRs can be finely tuned by varying silver ion concentrations or seed amounts. Also, both thick(diameter >30 nm) and thin(diameter <10 nm) GNRs with exceptional monodispersity can be well prepared by this method. These findings indicate that this method has a greater performance in controlling the morphology of GNRs than that of traditional approach with ascorbic acid as a reductant.