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2018 Volume 81 Issue 10
2018, 81(10): 867-879
Abstract:
The syntheses of magnetic nanoparticles (MNPs) have been intensively developed for both fundamental research and technological applications. Compared to the bulk magnet, MNPs exhibit unique magnetic property, which enables the modulation by systematic nanoscale engineering. In this review, the fundamental features and the syntheses of various MNPs, including magnetic metal, metallic alloy, metal oxide, and multifunctional MNPs were introduced. Especially the organic phase syntheses of MNPs with precise control over their sizes, shapes, compositions, and structures were focused on. Finally the applications of various MNPs in biomedicine were discussed.
The syntheses of magnetic nanoparticles (MNPs) have been intensively developed for both fundamental research and technological applications. Compared to the bulk magnet, MNPs exhibit unique magnetic property, which enables the modulation by systematic nanoscale engineering. In this review, the fundamental features and the syntheses of various MNPs, including magnetic metal, metallic alloy, metal oxide, and multifunctional MNPs were introduced. Especially the organic phase syntheses of MNPs with precise control over their sizes, shapes, compositions, and structures were focused on. Finally the applications of various MNPs in biomedicine were discussed.
2018, 81(10): 880-889
Abstract:
Arsenic in the natural environment is considered as one of the most serious environmental threats in the world. Long-term exposure to arsenic from drinking water can cause various diseases. Therefore, there is an urgent need to develop economically effective arsenic removal technology. Iron-based water treatment materials have attracted more attention on arsenic removal due to its good affinity to arsenic, strong reactivity on the surface, low cost, easy preparation and recycling. This paper summarizes the progress in arsenic removal technology by iron-based materials, such as ferric (hydr) oxide, zero-valent iron, iron-based multi-mental oxide and their composites. Possible influence factors and mechanisms of arsenic removal in aqueous solution by different iron-based water treatment materials were discussed in details. At the same time, the influence factors of arsenic desorption and the toxicity assessment of the above mentioned materials were summarized. Finally, the main problems about arsenic removal existed in present research are put forward. The prospects for the further development of iron-based water treatment materials for arsenic removal are also discussed.
Arsenic in the natural environment is considered as one of the most serious environmental threats in the world. Long-term exposure to arsenic from drinking water can cause various diseases. Therefore, there is an urgent need to develop economically effective arsenic removal technology. Iron-based water treatment materials have attracted more attention on arsenic removal due to its good affinity to arsenic, strong reactivity on the surface, low cost, easy preparation and recycling. This paper summarizes the progress in arsenic removal technology by iron-based materials, such as ferric (hydr) oxide, zero-valent iron, iron-based multi-mental oxide and their composites. Possible influence factors and mechanisms of arsenic removal in aqueous solution by different iron-based water treatment materials were discussed in details. At the same time, the influence factors of arsenic desorption and the toxicity assessment of the above mentioned materials were summarized. Finally, the main problems about arsenic removal existed in present research are put forward. The prospects for the further development of iron-based water treatment materials for arsenic removal are also discussed.
2018, 81(10): 890-895
Abstract:
Pathogenic microorganism is a kind of important microorganisms which affect human health. Nano electrochemical immune-biosensors have the advantages of fast detection, high sensitivity, low detection limit and low cost in the detection of pathogenic microorganisms. The research progress in several nano-material based electrochemical biosensors was reviewed in this paper. How to use different nano-materials to improve the electrochemical biosensors performance was analyzed. Different sensors' detecting results are compared and analyzed. Finally, the future development trend was prospected.
Pathogenic microorganism is a kind of important microorganisms which affect human health. Nano electrochemical immune-biosensors have the advantages of fast detection, high sensitivity, low detection limit and low cost in the detection of pathogenic microorganisms. The research progress in several nano-material based electrochemical biosensors was reviewed in this paper. How to use different nano-materials to improve the electrochemical biosensors performance was analyzed. Different sensors' detecting results are compared and analyzed. Finally, the future development trend was prospected.
2018, 81(10): 896-902
Abstract:
The increasing demand for bioactive compounds is mainly pushed by their wide range of nutritional and therapeutic benefits, especially in pharmaceutical and food industries. But the large-scale industrial application of bioactive compounds was limited by conventional production means. Laccase, as biocatalysts, is one of the encouraging potential enzymes for industrialization, which have demonstrated high efficiency in the synthesis of bioactive compounds under mild conditions. This review summarizes the application of this interesting enzyme in synthesizing bioactive compounds in the last decade, and also introduces the enzyme structure and the catalytic mechanism relevant to their application as biocatalysts. In addition, the review also comprises a discussion of the hurdles, such as lack of sufficient enzyme stocks and some laccase mediator systems are inapplicable for industrialization, etc, in industrialized application of laccase. Finally, the key areas for future research are pointed out which include enhancing output of laccase by heterologous expression, improving lifetime of laccase by immobilization and protein engineering and cutting cost of application by developing more effective and inexpensive mediator coupled with the search of new substrates.
The increasing demand for bioactive compounds is mainly pushed by their wide range of nutritional and therapeutic benefits, especially in pharmaceutical and food industries. But the large-scale industrial application of bioactive compounds was limited by conventional production means. Laccase, as biocatalysts, is one of the encouraging potential enzymes for industrialization, which have demonstrated high efficiency in the synthesis of bioactive compounds under mild conditions. This review summarizes the application of this interesting enzyme in synthesizing bioactive compounds in the last decade, and also introduces the enzyme structure and the catalytic mechanism relevant to their application as biocatalysts. In addition, the review also comprises a discussion of the hurdles, such as lack of sufficient enzyme stocks and some laccase mediator systems are inapplicable for industrialization, etc, in industrialized application of laccase. Finally, the key areas for future research are pointed out which include enhancing output of laccase by heterologous expression, improving lifetime of laccase by immobilization and protein engineering and cutting cost of application by developing more effective and inexpensive mediator coupled with the search of new substrates.
2018, 81(10): 903-908
Abstract:
Natural gas dehydration is an integral part of the natural gas purification process, and appropriate dewatering techniques and processes are of paramount importance. In this paper, the characteristics of emerging membrane separation methods for natural gas dehydration, the characterization parameters and testing of membrane separation performance as well as the design of membrane modules and the selection of operating conditions are briefly introduced. Polymer membrane materials and zeolite membrane materials are also introduced. Finally, the application potential of metal organic framework (MOF) materials and the future development trend of natural gas dehydration technology are predicted.
Natural gas dehydration is an integral part of the natural gas purification process, and appropriate dewatering techniques and processes are of paramount importance. In this paper, the characteristics of emerging membrane separation methods for natural gas dehydration, the characterization parameters and testing of membrane separation performance as well as the design of membrane modules and the selection of operating conditions are briefly introduced. Polymer membrane materials and zeolite membrane materials are also introduced. Finally, the application potential of metal organic framework (MOF) materials and the future development trend of natural gas dehydration technology are predicted.
2018, 81(10): 909-913
Abstract:
Colloidal photonic crystals have been widely developed due to their novel optical properties, easy-preparation and low-cost. The structural color of colloidal photonic crystals is highly related to the refractive index and size of the microspheres. But the structural color is tuned mainly based on the controlling of the size instead of the refractive index of the microspheres. Herein, we developed a novel strategy to tune the refractive indexes and thus the structural colors of colloidal photonic crystals by doping different amounts of TiO2 nanoparticles into polystyrene (PS) microspheres. Finally, colorful photonic crystal patterns were successfully printed with the aqueous colloid solution of these as-prepared TiO2-PS microspheres as ink. This facile fabrication strategy will be easy to be extended to other composite microspheres by doping different inorganic nanoparticles with different refractive indexes.
Colloidal photonic crystals have been widely developed due to their novel optical properties, easy-preparation and low-cost. The structural color of colloidal photonic crystals is highly related to the refractive index and size of the microspheres. But the structural color is tuned mainly based on the controlling of the size instead of the refractive index of the microspheres. Herein, we developed a novel strategy to tune the refractive indexes and thus the structural colors of colloidal photonic crystals by doping different amounts of TiO2 nanoparticles into polystyrene (PS) microspheres. Finally, colorful photonic crystal patterns were successfully printed with the aqueous colloid solution of these as-prepared TiO2-PS microspheres as ink. This facile fabrication strategy will be easy to be extended to other composite microspheres by doping different inorganic nanoparticles with different refractive indexes.
2018, 81(10): 914-918, 923
Abstract:
Chitosan was prepared from waste shrimp shell, and then nano-Fe3O4@chitosan material was prepared by using chitosan as shell, magnetic Fe3O4 as core, liquid paraffin as dispersant, T-80 as emulsifier and glutaraldehyde as crosslinking agent. The prepared nano material was characterized by IR, SEM, TG, and XRD. The results showed that the surface of nano-Fe3O4@chitosan are smooth and spherical, the mass ratio of chitosan to Fe3O4 is 2:1 and the diameter is about 75.82 nm. Adsorption kinetic experiment showed that the Cu2+ adsorption of nano-Fe3O4@chitosan corresponds to pseudo-second-order kinetic, which implies a dominant chemical adsorption. The equilibrium adsorption capacity was 17.32 mg/g. Adsorption isotherm experiment showed that the adsorption conforms to the Freundlic adsorption isotherm model, and there is strong interaction between nano-Fe3O4@chitosan and Cu2+. The maximum adsorption capacity was 213.68 mg/g.
Chitosan was prepared from waste shrimp shell, and then nano-Fe3O4@chitosan material was prepared by using chitosan as shell, magnetic Fe3O4 as core, liquid paraffin as dispersant, T-80 as emulsifier and glutaraldehyde as crosslinking agent. The prepared nano material was characterized by IR, SEM, TG, and XRD. The results showed that the surface of nano-Fe3O4@chitosan are smooth and spherical, the mass ratio of chitosan to Fe3O4 is 2:1 and the diameter is about 75.82 nm. Adsorption kinetic experiment showed that the Cu2+ adsorption of nano-Fe3O4@chitosan corresponds to pseudo-second-order kinetic, which implies a dominant chemical adsorption. The equilibrium adsorption capacity was 17.32 mg/g. Adsorption isotherm experiment showed that the adsorption conforms to the Freundlic adsorption isotherm model, and there is strong interaction between nano-Fe3O4@chitosan and Cu2+. The maximum adsorption capacity was 213.68 mg/g.
2018, 81(10): 919-923
Abstract:
Fluorophores with aggregation-induced emission (AIE) activity has wide application prospects for the detection of trace amount of uranyl ions. In this study, a tetraphenylethylene derivative T2 was synthesized. The optical properties of the solution and aggregation states were characterized, which indicated that T2 shows obvious AIE feature. Moreover, the preliminary studies showed that compound T2 can coordinate with uranyl ion, along with the blue shift of fluorescence emission from 540 nm to 500 nm, and the obvious color change from yellow to yellow-green. The results indicated that compound T2 has the potential to detect uranyl ion in water.
Fluorophores with aggregation-induced emission (AIE) activity has wide application prospects for the detection of trace amount of uranyl ions. In this study, a tetraphenylethylene derivative T2 was synthesized. The optical properties of the solution and aggregation states were characterized, which indicated that T2 shows obvious AIE feature. Moreover, the preliminary studies showed that compound T2 can coordinate with uranyl ion, along with the blue shift of fluorescence emission from 540 nm to 500 nm, and the obvious color change from yellow to yellow-green. The results indicated that compound T2 has the potential to detect uranyl ion in water.
2018, 81(10): 924-928
Abstract:
Catechol and hydroquinone are very important fine chemical intermediate products. They have a wide range of applications in all industries. It is a mild and environment-friendly route to produce dihydroxybenzene through the reaction of phenol with hydrogen peroxide. The choice of the catalyst and the optimization of the reaction conditions are very important to the route. HMS modified by iron (Fe/HMS) is used as a catalyst. Effects of Fe contents in Fe/HMS, catalyst amount, temperature and reaction time on the catalytic performances were examined. Under the conditions of water solvent, n(Fe)/n(Si) of 0.04, ratio of phenol to H2O2 of 2:1, reaction temperature of 50℃, amount of catalyst of 0.1 g and reaction time of 4 hours, phenol conversion of 45.5% and the dihydroxybenzene selectivity of 94.9% are achieved. The results of the N2 absorption-desorption isotherms illustrates that Fe/HMS material has a uniform mesoporous structure, and Fe is successfully incorporated into the framework of HMS. The catalyst has good stability, and its skeleton remains intact after recycling.
Catechol and hydroquinone are very important fine chemical intermediate products. They have a wide range of applications in all industries. It is a mild and environment-friendly route to produce dihydroxybenzene through the reaction of phenol with hydrogen peroxide. The choice of the catalyst and the optimization of the reaction conditions are very important to the route. HMS modified by iron (Fe/HMS) is used as a catalyst. Effects of Fe contents in Fe/HMS, catalyst amount, temperature and reaction time on the catalytic performances were examined. Under the conditions of water solvent, n(Fe)/n(Si) of 0.04, ratio of phenol to H2O2 of 2:1, reaction temperature of 50℃, amount of catalyst of 0.1 g and reaction time of 4 hours, phenol conversion of 45.5% and the dihydroxybenzene selectivity of 94.9% are achieved. The results of the N2 absorption-desorption isotherms illustrates that Fe/HMS material has a uniform mesoporous structure, and Fe is successfully incorporated into the framework of HMS. The catalyst has good stability, and its skeleton remains intact after recycling.
2018, 81(10): 934-938
Abstract:
1α-hydroxydehydroepiandrosterone was prepared from androsta-1, 4-diene-3, 17-dione through six steps including protection of carbonyl group, bromination, elimination, oxidation, incomplete hydrogenation and deprotection, with an overall yield of 29%. The method has the advantages of easily available raw materials, conventional reagents, mild reaction conditions, simple operation and lays a foundation for industrialized production of 1α-Hydroxydehydroepiandrosterone and the synthesis of vitamin D drugs.
1α-hydroxydehydroepiandrosterone was prepared from androsta-1, 4-diene-3, 17-dione through six steps including protection of carbonyl group, bromination, elimination, oxidation, incomplete hydrogenation and deprotection, with an overall yield of 29%. The method has the advantages of easily available raw materials, conventional reagents, mild reaction conditions, simple operation and lays a foundation for industrialized production of 1α-Hydroxydehydroepiandrosterone and the synthesis of vitamin D drugs.
2018, 81(10): 944-950
Abstract:
HY/ZSM-5 composite zeolite was prepared by hydrothermal method and characterized by XRD, SEM, N2-adsorption, NH3-TPD and Py-FTIR. The results indicated that HY was completely encapsulated by HZSM-5 and formed a core-shell morphology of HY/ZSM-5 composite zeolite. Compared with the mechanical mixture, the composite zeolites show lower microporous surface area and microporous volume, higher quantity of total and strong acid sites, lower quantity of weak acid sites, the similar Br nsted acid amount and the reduced Lewis acid amount. Cellulose was hydrolyzed in 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) using HY/ZSM-5 as catalyst. Compared with the hydrolysis of cellulose catalyzed by HY zeolite, the optimal glucose yield could be significantly improved from 28.04% to 38.78%, and the glucose selectivity improved from 28.91% to 48.29%.
HY/ZSM-5 composite zeolite was prepared by hydrothermal method and characterized by XRD, SEM, N2-adsorption, NH3-TPD and Py-FTIR. The results indicated that HY was completely encapsulated by HZSM-5 and formed a core-shell morphology of HY/ZSM-5 composite zeolite. Compared with the mechanical mixture, the composite zeolites show lower microporous surface area and microporous volume, higher quantity of total and strong acid sites, lower quantity of weak acid sites, the similar Br nsted acid amount and the reduced Lewis acid amount. Cellulose was hydrolyzed in 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) using HY/ZSM-5 as catalyst. Compared with the hydrolysis of cellulose catalyzed by HY zeolite, the optimal glucose yield could be significantly improved from 28.04% to 38.78%, and the glucose selectivity improved from 28.91% to 48.29%.
2018, 81(10): 951-956
Abstract:
The aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH2), POSS grafted polyethylene glycol (POSS-PEG) and POSS grafted poly(lactic acid) (POSS-g-PLLA) were blended with poly(L-lactic acid)(PLLA) by solution blending method in dichloromethane, then the POSS-NH2/PLLA, POSS-PEG/PLLA and POSS-g-PLLA/PLLA composites with different mass fraction of POSS were obtained. The differential scanning calorimetry (DSC) and differential polarizing microscope (POM) were used to investigate the crystallization behavior in bulk, the crystallization morphology and the growth rate of composites, respectively. The results showed that the crystallization ability of PLLA is improved by the adding of POSS-PEG with mass percentage of 1(wt)%, 5(wt)% and 10(wt)%. However, POSS-NH2 and POSS-g-PLLA will improves the crystallization ability of PLLA when the POSS have larger mass contents (5(wt)% and 10(wt)%). Based on the POM observation, it can be found that addition of POSS-PEG promotes the spherulite growth rate of PLLA.
The aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH2), POSS grafted polyethylene glycol (POSS-PEG) and POSS grafted poly(lactic acid) (POSS-g-PLLA) were blended with poly(L-lactic acid)(PLLA) by solution blending method in dichloromethane, then the POSS-NH2/PLLA, POSS-PEG/PLLA and POSS-g-PLLA/PLLA composites with different mass fraction of POSS were obtained. The differential scanning calorimetry (DSC) and differential polarizing microscope (POM) were used to investigate the crystallization behavior in bulk, the crystallization morphology and the growth rate of composites, respectively. The results showed that the crystallization ability of PLLA is improved by the adding of POSS-PEG with mass percentage of 1(wt)%, 5(wt)% and 10(wt)%. However, POSS-NH2 and POSS-g-PLLA will improves the crystallization ability of PLLA when the POSS have larger mass contents (5(wt)% and 10(wt)%). Based on the POM observation, it can be found that addition of POSS-PEG promotes the spherulite growth rate of PLLA.
2018, 81(10): 929-933
Abstract:
Lignosulfonic acid is a kind of heterogeneous, environmentally friendly, biomass-based solid catalyst. In this paper, it was prepared by ion-exchange method using sodium lignosulfonate in papermaking waste as raw material. Its structure was characterized by FT-IR, elemental analysis and titration. Using lignosulfonic acid as a catalyst, N-substituted pyrroles were synthesized efficiently by Paal-Knorr reaction of hexane-2, 5-dione and primary amine in good to excellent yields. This is a typical nucleophilic reaction. The stronger the nucleophilic ability of the primary amine, the more easily the reaction proceeds.
Lignosulfonic acid is a kind of heterogeneous, environmentally friendly, biomass-based solid catalyst. In this paper, it was prepared by ion-exchange method using sodium lignosulfonate in papermaking waste as raw material. Its structure was characterized by FT-IR, elemental analysis and titration. Using lignosulfonic acid as a catalyst, N-substituted pyrroles were synthesized efficiently by Paal-Knorr reaction of hexane-2, 5-dione and primary amine in good to excellent yields. This is a typical nucleophilic reaction. The stronger the nucleophilic ability of the primary amine, the more easily the reaction proceeds.
2018, 81(10): 939-943, 938
Abstract:
Densities of two aqueous ternary systems Li2SO4-Na2SO4-H2O, The experimental study of these systems were carried out for four total ionic strengths ranging from 0.1 to 4.5 mol·kg-1. For each total ionic strength, the values of the ionic strength fraction of the Na2SO4 and K2SO4 were y2≈0.2, 0.4, 0.6, and 0.8. The Pitzer mixing parameters θV and ψV for the ternary systems were fit for the experimental density values. Also, using the Pitzer model, we determined the volume of mixing at constant ionic strength at 298.15 K, for each ternary system that have been studied.
Densities of two aqueous ternary systems Li2SO4-Na2SO4-H2O, The experimental study of these systems were carried out for four total ionic strengths ranging from 0.1 to 4.5 mol·kg-1. For each total ionic strength, the values of the ionic strength fraction of the Na2SO4 and K2SO4 were y2≈0.2, 0.4, 0.6, and 0.8. The Pitzer mixing parameters θV and ψV for the ternary systems were fit for the experimental density values. Also, using the Pitzer model, we determined the volume of mixing at constant ionic strength at 298.15 K, for each ternary system that have been studied.
2018, 81(10): 957-959
Abstract:
3-Keto-4-carbomethoxythiophane (Ⅲ) was synthesized by Dieckmann cyclization reaction, using methanol and mercapto acetic acid as the starting materials. The structure of the product was confirmed by 1H NMR, 13C NMR and HRMS. Effects of different organic or inorganic base types, reaction solvent and temperature on the cyclization reaction were investigated as well. The results showed that organic bases are superior to inorganic bases; high temperature is beneficial to give Ⅲ. The optimized process for the synthesis of compound Ⅲ is as follows:pyridine as base, toluene as solvent, react at 80℃ for 2 h. The yield of 3-Keto-4-carbomethoxythiophane reached 78%.
3-Keto-4-carbomethoxythiophane (Ⅲ) was synthesized by Dieckmann cyclization reaction, using methanol and mercapto acetic acid as the starting materials. The structure of the product was confirmed by 1H NMR, 13C NMR and HRMS. Effects of different organic or inorganic base types, reaction solvent and temperature on the cyclization reaction were investigated as well. The results showed that organic bases are superior to inorganic bases; high temperature is beneficial to give Ⅲ. The optimized process for the synthesis of compound Ⅲ is as follows:pyridine as base, toluene as solvent, react at 80℃ for 2 h. The yield of 3-Keto-4-carbomethoxythiophane reached 78%.
