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2019 Volume 82 Issue 1
2019, 82(1): 3-11
Abstract:
Zero-valent iron (ZVI) technology has been widely used in wastewater treatment due to its high efficiency and economy. The recent research on ZVI was divided into two major directions:one is to explore the modification of ZVI, including its particle size, internal structure change, and the combination of ZVI and other metals; the other is to study the mechanism of ZVI removing different contaminants, including the reducibility of ZVI, adsorption precipitation of the FeOOH, ZVI promoted Fenton reaction, etc. This paper firstly summarized the recent advances of ZVI-based water treatment methods including sponge iron, nZVI, doping of ZVI with other metals (micro-electrolysis method), combination of ZVI with Fenton-based oxidation. Then, the reaction mechanism of the above methods for removing heavy metals, arsenic, nitrates, dyes and phenol was discussed, and it was pointed out that ZVI materials have appreciable removal efficiency for several types of pollutants. Finally, the future perspectives regarding the application of ZVI in treating wastewater was proposed.
Zero-valent iron (ZVI) technology has been widely used in wastewater treatment due to its high efficiency and economy. The recent research on ZVI was divided into two major directions:one is to explore the modification of ZVI, including its particle size, internal structure change, and the combination of ZVI and other metals; the other is to study the mechanism of ZVI removing different contaminants, including the reducibility of ZVI, adsorption precipitation of the FeOOH, ZVI promoted Fenton reaction, etc. This paper firstly summarized the recent advances of ZVI-based water treatment methods including sponge iron, nZVI, doping of ZVI with other metals (micro-electrolysis method), combination of ZVI with Fenton-based oxidation. Then, the reaction mechanism of the above methods for removing heavy metals, arsenic, nitrates, dyes and phenol was discussed, and it was pointed out that ZVI materials have appreciable removal efficiency for several types of pollutants. Finally, the future perspectives regarding the application of ZVI in treating wastewater was proposed.
2019, 82(1): 12-17
Abstract:
With the development of nucleus industry, the removal of radioactive liquid waste has been paid more and more attention. The research progress in the methods including ion exchange, solvent extraction, adsorption method, membrane separation, chemical precipitation and combination processes, which have been frequently used for removing radioactive liquid waste containing cesium were summarized in this paper. The advantages and disadvantages of various methods were compared, and the future direction of methods for the removal of radioactive cesium was also discussed. The paper has great reference value for the removal of radioactive cesium for radioactive pollution in different situations.
With the development of nucleus industry, the removal of radioactive liquid waste has been paid more and more attention. The research progress in the methods including ion exchange, solvent extraction, adsorption method, membrane separation, chemical precipitation and combination processes, which have been frequently used for removing radioactive liquid waste containing cesium were summarized in this paper. The advantages and disadvantages of various methods were compared, and the future direction of methods for the removal of radioactive cesium was also discussed. The paper has great reference value for the removal of radioactive cesium for radioactive pollution in different situations.
2019, 82(1): 18-26
Abstract:
As a new type of separating medium, high performance liquid chromatography (HPLC) monolithic columns have attracted considerable attention on account of its own characteristics, such as the simple preparation process, easy to be modified and excellent separation properties. Especially, due to its favorable biocompatibility, high column efficiency, long life, wide of the raw material source, good repeatability, unrestricted by pH, polymer-based monolithic columns are frequently used to separate and detect some small molecules compounds and proteins in food, chemical industry, agriculture, environment and biomedical science, which have shown a promising application prospect. Refer to the latest reports about HPLC, this review will focus on the research achievements of the preparation, modification method and application of monolithic columns in recent ten years. In addition, the future prospects for development regarding monolithic columns in various fields are also expected.
As a new type of separating medium, high performance liquid chromatography (HPLC) monolithic columns have attracted considerable attention on account of its own characteristics, such as the simple preparation process, easy to be modified and excellent separation properties. Especially, due to its favorable biocompatibility, high column efficiency, long life, wide of the raw material source, good repeatability, unrestricted by pH, polymer-based monolithic columns are frequently used to separate and detect some small molecules compounds and proteins in food, chemical industry, agriculture, environment and biomedical science, which have shown a promising application prospect. Refer to the latest reports about HPLC, this review will focus on the research achievements of the preparation, modification method and application of monolithic columns in recent ten years. In addition, the future prospects for development regarding monolithic columns in various fields are also expected.
2019, 82(1): 27-31
Abstract:
Foodborne pathogenic bacteria are harmful to human health. However, due to its small amount in the food matrix, the pathogenic bacteria usually need to be enriched before detection. As a common pretreatment, magnetic separation shows excellent application prospect in the enrichment and separation of pathogenic bacteria. There are many kinds of recognition agents used in magnetic separation. In this paper, the application of several main recognition agents, including antibodies, antibiotics, nucleic acids and lectins in application of magnetic separation were reviewed.
Foodborne pathogenic bacteria are harmful to human health. However, due to its small amount in the food matrix, the pathogenic bacteria usually need to be enriched before detection. As a common pretreatment, magnetic separation shows excellent application prospect in the enrichment and separation of pathogenic bacteria. There are many kinds of recognition agents used in magnetic separation. In this paper, the application of several main recognition agents, including antibodies, antibiotics, nucleic acids and lectins in application of magnetic separation were reviewed.
2019, 82(1): 32-36
Abstract:
Due to their abundant structures, high stability and excellent catalytic properties, palladacycles complexes have become one of the hotspots in the research of palladium chemistry. A number of synthesis methods have been developed, such as C-H bond activation, oxidation addition, metal transfer, nucleophilic addition, and ligand exchange. The CY type palladacycles complexes from ternary ring to eleven-membered ring and YCY type palladacycles complexes have been afforded. Palladacycles complexes have been utilized in olefin hydrogenation, coupling reaction, asymmetric catalysis, and other reactions. In this article, the types of palladacycles complexes were briefly introduced. The synthesis methods and application for catalytic reactions of palladacycles complexes were focused on. The development suggestions of palladacycles complexes for synthesis and catalytic application were proposed.
Due to their abundant structures, high stability and excellent catalytic properties, palladacycles complexes have become one of the hotspots in the research of palladium chemistry. A number of synthesis methods have been developed, such as C-H bond activation, oxidation addition, metal transfer, nucleophilic addition, and ligand exchange. The CY type palladacycles complexes from ternary ring to eleven-membered ring and YCY type palladacycles complexes have been afforded. Palladacycles complexes have been utilized in olefin hydrogenation, coupling reaction, asymmetric catalysis, and other reactions. In this article, the types of palladacycles complexes were briefly introduced. The synthesis methods and application for catalytic reactions of palladacycles complexes were focused on. The development suggestions of palladacycles complexes for synthesis and catalytic application were proposed.
2019, 82(1): 37-43
Abstract:
Silylation protection of hydroxyl groups within alcohol and phenol is an important class of organic synthesis, which means to stabilize the hydroxyl groups and eliminate or mitigate the side reactions caused by them. The smaller steric hindrance of the group attached to the silicon atom in the protecting group, the greater reactivity of the protecting group, and the worse stability of the corresponding silyl ether be formed. It can be removed under weak acid or weak base conditions. The larger steric hindrance of the group attached to the silicon atom, the smaller reactivity of the protecting group, and the more difficult of silylation reaction, which requires the use of a catalyst. This article describes the types of organosilane protecting groups, such as trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, phenyl-substituted silane and bridging silane. The activity and stability of the protecting group under different environments are also discussed.
Silylation protection of hydroxyl groups within alcohol and phenol is an important class of organic synthesis, which means to stabilize the hydroxyl groups and eliminate or mitigate the side reactions caused by them. The smaller steric hindrance of the group attached to the silicon atom in the protecting group, the greater reactivity of the protecting group, and the worse stability of the corresponding silyl ether be formed. It can be removed under weak acid or weak base conditions. The larger steric hindrance of the group attached to the silicon atom, the smaller reactivity of the protecting group, and the more difficult of silylation reaction, which requires the use of a catalyst. This article describes the types of organosilane protecting groups, such as trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, phenyl-substituted silane and bridging silane. The activity and stability of the protecting group under different environments are also discussed.
2019, 82(1): 44-50
Abstract:
Developing a smart fluorescent probe which can specifically and sensitively detect matrix metalloproteinases-2 (MMP-2) is vital for the early accurate diagnosis and treatment of cancers. In this study, fluorescein isothiocyanate (FITC) was firstly conjugated to the peptide substrate GPLGVRGY by using copper (I)-catalyzed "click" reaction, and subsequently reacted with gold nanorods decorated with SH-PEG-COOH under the catalysis of EDC and Sulfo-NHS through amidation reaction to afford a novel fluorescence resonance energy transfer (FRET)-based probe GNR@FITC for specific detection of MMP-2. In vitro enzyme detection experiments, MTT assays and fluorescence imaging results showed that the probe shows good specificity and high sensitivity for the detection of MMP-2-overexpressed 4T1 cells, which may have great potential for clinical application in early diagnosis of breast cancer.
Developing a smart fluorescent probe which can specifically and sensitively detect matrix metalloproteinases-2 (MMP-2) is vital for the early accurate diagnosis and treatment of cancers. In this study, fluorescein isothiocyanate (FITC) was firstly conjugated to the peptide substrate GPLGVRGY by using copper (I)-catalyzed "click" reaction, and subsequently reacted with gold nanorods decorated with SH-PEG-COOH under the catalysis of EDC and Sulfo-NHS through amidation reaction to afford a novel fluorescence resonance energy transfer (FRET)-based probe GNR@FITC for specific detection of MMP-2. In vitro enzyme detection experiments, MTT assays and fluorescence imaging results showed that the probe shows good specificity and high sensitivity for the detection of MMP-2-overexpressed 4T1 cells, which may have great potential for clinical application in early diagnosis of breast cancer.
2019, 82(1): 51-55, 50
Abstract:
Three-dimensional NiO/CoMoO4 composite electrode materials were successfully prepared by two-step hydrothermal and high temperature annealing. The structure, surface morphology and electrochemical performance were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electrochemical method. The results showed that NiO/CoMoO4 composite materials owned typical nanowires/nanosheet structure, which were different from needle-like morphology of NiO. The structure provided more active sites for the active substance, compared with pure NiO. The specific capacitance of the composites could reach 2253 F/g at the current density of 0.3 A/g, which was higher than that of pure NiO. It displayed good cycling stability with 92% capacitance retention after 2000 cycles due to the synergistic effect between NiO and CoMoO4.
Three-dimensional NiO/CoMoO4 composite electrode materials were successfully prepared by two-step hydrothermal and high temperature annealing. The structure, surface morphology and electrochemical performance were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electrochemical method. The results showed that NiO/CoMoO4 composite materials owned typical nanowires/nanosheet structure, which were different from needle-like morphology of NiO. The structure provided more active sites for the active substance, compared with pure NiO. The specific capacitance of the composites could reach 2253 F/g at the current density of 0.3 A/g, which was higher than that of pure NiO. It displayed good cycling stability with 92% capacitance retention after 2000 cycles due to the synergistic effect between NiO and CoMoO4.
2019, 82(1): 56-62
Abstract:
In this paper, magnetic hydrotalcite-like compound modified with sodium dodecylsulfate (Fe3O4@(SDS-HTlc)) nanocomposite was prepared by ion-exchange method. The samples were characterized by transmission electron microscope, powder X ray diffractometer, infrared spectrometer, elemental analysis etc. The adsorption property of Fe3O4@(SDS-HTlc) nanocomposite for methyl orange was studied by adsorption kinetics and thermodynamics. The experimental results showed that the adsorption kinetics conforms to the pseudo-second-order kinetic equation, and the adsorption isotherm agrees well with the linear equation. The adsorption amount of Fe3O4@(SDS-HTlc) for methyl orange decreased with increasing pH (and temperature). Fe3O4@(SDS-HTlc) nanocomposite can be easily separated from aqueous solution by the external magnetic field in 30 s, which provides a simple single step adsorption treatment option for removing dyes from water.
In this paper, magnetic hydrotalcite-like compound modified with sodium dodecylsulfate (Fe3O4@(SDS-HTlc)) nanocomposite was prepared by ion-exchange method. The samples were characterized by transmission electron microscope, powder X ray diffractometer, infrared spectrometer, elemental analysis etc. The adsorption property of Fe3O4@(SDS-HTlc) nanocomposite for methyl orange was studied by adsorption kinetics and thermodynamics. The experimental results showed that the adsorption kinetics conforms to the pseudo-second-order kinetic equation, and the adsorption isotherm agrees well with the linear equation. The adsorption amount of Fe3O4@(SDS-HTlc) for methyl orange decreased with increasing pH (and temperature). Fe3O4@(SDS-HTlc) nanocomposite can be easily separated from aqueous solution by the external magnetic field in 30 s, which provides a simple single step adsorption treatment option for removing dyes from water.
2019, 82(1): 63-67, 31
Abstract:
A hierarchical porous zinc oxide (ZnO) nanomaterials have been synthesized using rape flower pollen as a biological template, Zn(NO3)2 as a zinc source. The morphology and structure of the as-prepared samples were characterized by means of SEM, TEM, XRD, FTIR, etc. Experimental results showed that the pollen templated ZnO nanomaterials were hexagonal wurtzite structure, and faithfully duplicated the porous network structure of the template. Meantime, the effects of preparation conditions such as calcination temperature and reactant concentration on the structure, morphology and scale of the product were studied.
A hierarchical porous zinc oxide (ZnO) nanomaterials have been synthesized using rape flower pollen as a biological template, Zn(NO3)2 as a zinc source. The morphology and structure of the as-prepared samples were characterized by means of SEM, TEM, XRD, FTIR, etc. Experimental results showed that the pollen templated ZnO nanomaterials were hexagonal wurtzite structure, and faithfully duplicated the porous network structure of the template. Meantime, the effects of preparation conditions such as calcination temperature and reactant concentration on the structure, morphology and scale of the product were studied.
2019, 82(1): 74-79
Abstract:
Based on 4-amino-2-methylpyrimidine-5-carbonitrile as raw material, twelve 2-methyl-5-(5-substitutional-1, 3, 4-oxadiazol/thiadiazole-3-yl)pyrimidin-4-amine compounds were synthesized through five step reactions including hydrolysis, esterification, hydrazidation, cyclization and thioetherification. The structures of titled compounds were characterized by 1H NMR, 13C NMR, MS and elemental analysis. Preliminary bioassay results showed that compounds 6f and 6f' have moderate inhibitory activities against S. sclerotiorum, P. infestans, T. cucumeris and G. zeae at the concerntration of 50 μg/mL, which are comparable to that of Azoxystrobin.
Based on 4-amino-2-methylpyrimidine-5-carbonitrile as raw material, twelve 2-methyl-5-(5-substitutional-1, 3, 4-oxadiazol/thiadiazole-3-yl)pyrimidin-4-amine compounds were synthesized through five step reactions including hydrolysis, esterification, hydrazidation, cyclization and thioetherification. The structures of titled compounds were characterized by 1H NMR, 13C NMR, MS and elemental analysis. Preliminary bioassay results showed that compounds 6f and 6f' have moderate inhibitory activities against S. sclerotiorum, P. infestans, T. cucumeris and G. zeae at the concerntration of 50 μg/mL, which are comparable to that of Azoxystrobin.
2019, 82(1): 80-86
Abstract:
A molecularly imprinted solid phase extraction membrane with high selectivity to pyrethroid was prepared by in situ polymerization using cyhalothrin as template molecule, ethylene glycol dimethacrylate as the cross linking agent and acetonitrile as porogenic agent, and the performance and application of as-prepared molecularly imprinted membrane were investigated. Ultraviolet spectroscopy was used to study the selection of functional monomer and the concentration ratio of functional monomer to template molecule. This molecularly imprinted membrane was used to enrich and cleanse pyrethrin pesticide residues in samples. The results showed that the membrane had strong specific adsorption and enrichment capacity for pyrethrin pesticides. The detection limits were 0.01μg/mL for cyhalothrin and bifenthrin, 0.05μg/mL for tetramethrin, beta cypermethrin, dimefluthrin and fenvalerate. The average recoveries of the spiked samples were between 83.4% and 95.9%, the relative standard deviations were 1.45%~3.76% (n=5). The method is simple, sensitive, accurate and reliable.
A molecularly imprinted solid phase extraction membrane with high selectivity to pyrethroid was prepared by in situ polymerization using cyhalothrin as template molecule, ethylene glycol dimethacrylate as the cross linking agent and acetonitrile as porogenic agent, and the performance and application of as-prepared molecularly imprinted membrane were investigated. Ultraviolet spectroscopy was used to study the selection of functional monomer and the concentration ratio of functional monomer to template molecule. This molecularly imprinted membrane was used to enrich and cleanse pyrethrin pesticide residues in samples. The results showed that the membrane had strong specific adsorption and enrichment capacity for pyrethrin pesticides. The detection limits were 0.01μg/mL for cyhalothrin and bifenthrin, 0.05μg/mL for tetramethrin, beta cypermethrin, dimefluthrin and fenvalerate. The average recoveries of the spiked samples were between 83.4% and 95.9%, the relative standard deviations were 1.45%~3.76% (n=5). The method is simple, sensitive, accurate and reliable.
2019, 82(1): 87-91
Abstract:
In forensic science, it is particularly important for the rapid detection of traffic accidents and some lawsuits to identify the tire rubber. A method, non-destructive identification of tire rubber based on infrared spectroscopy and radial basis function neural network, is proposed based on the problem of traditional sampling and analysis techniques would destroy the physical evidence and the comprehensive consideration of multi-variable and multi-dimensional differences in samples. Samples of different brands were collected, and their spectra were automatically baseline corrected and normalized, and were smoothed using the Savitsky-Golay algorithm. Dimension reduction method is used to achieve efficient screening of 840 original features to 5 identification features. Using cross-validation of training samples for test samples and selecting the K value of 1, "Feature 3" as the main independent variable, and "Feature 4", "Feature 5", "Feature 2", and "Feature 1" as covariates as classification parameters. A classification model was established through calculating the distance between samples according to the weighted feature of importance. The total classification accuracy rate is 83.56%, and the differentiation effect is good. Finally, 73 samples were successfully divided into 10 categories. The results showed that combing the IR spectral detection and KNN can identify the tire rubber spectra. The method has strong universality and high efficiency, and can provide certain reference significance.
In forensic science, it is particularly important for the rapid detection of traffic accidents and some lawsuits to identify the tire rubber. A method, non-destructive identification of tire rubber based on infrared spectroscopy and radial basis function neural network, is proposed based on the problem of traditional sampling and analysis techniques would destroy the physical evidence and the comprehensive consideration of multi-variable and multi-dimensional differences in samples. Samples of different brands were collected, and their spectra were automatically baseline corrected and normalized, and were smoothed using the Savitsky-Golay algorithm. Dimension reduction method is used to achieve efficient screening of 840 original features to 5 identification features. Using cross-validation of training samples for test samples and selecting the K value of 1, "Feature 3" as the main independent variable, and "Feature 4", "Feature 5", "Feature 2", and "Feature 1" as covariates as classification parameters. A classification model was established through calculating the distance between samples according to the weighted feature of importance. The total classification accuracy rate is 83.56%, and the differentiation effect is good. Finally, 73 samples were successfully divided into 10 categories. The results showed that combing the IR spectral detection and KNN can identify the tire rubber spectra. The method has strong universality and high efficiency, and can provide certain reference significance.
2019, 82(1): 68-73
Abstract:
A series of 5-arylidene-2, 3-diaryl-thiazolidin-4-one derivatives (4a~4r) were synthesized from 2, 3-diphenyl-thiazolidin-4-one via microwave irradiation, and evaluated in vitro at the concentration of 100μg/mL against seven phytopathogenic fungi, namely Fusarium graminearum, Alternaria alternata, Fusarium oxysporium f. sp. vasinfectum, Pyricularia oryzae, Valsa mali, Alternaria solani and Alternaria brassicae. All the prepared compounds were characterized for structural confirmation by melting point, 1H NMR, and MS. The activity results indicated that 4g and 4n exhibit potential antifungal activities against the phytopathogenic fungi.
A series of 5-arylidene-2, 3-diaryl-thiazolidin-4-one derivatives (4a~4r) were synthesized from 2, 3-diphenyl-thiazolidin-4-one via microwave irradiation, and evaluated in vitro at the concentration of 100μg/mL against seven phytopathogenic fungi, namely Fusarium graminearum, Alternaria alternata, Fusarium oxysporium f. sp. vasinfectum, Pyricularia oryzae, Valsa mali, Alternaria solani and Alternaria brassicae. All the prepared compounds were characterized for structural confirmation by melting point, 1H NMR, and MS. The activity results indicated that 4g and 4n exhibit potential antifungal activities against the phytopathogenic fungi.
2019, 82(1): 92-95
Abstract:
The benzofuran skeleton widely exists in natural products and synthetic medicines. Many benzofuran derivatives have important physiological, pharmacological and toxicological activities, and their synthesis methods have attracted much attention. A method of "one pot" synthesis ethyl benzofuran-3-carboxylate was obtained:in the presence of Et3N, toluene was used as a solvent, the mole ratio of o-iodophenol to ethyl propiolate was 1:1.5, and the reaction was carried out at room temperature for 20 min; then adding K2CO3, Pd(OAc)2/PPh3 85℃ for 3.5h, the product yield reached 78%. By improving the synthesis method, the process avoids the use of highly toxic diazo compound, and has the advantages of less steps, short time, simple operation and high yield. The method reported in this paper has implications for the synthesis of similar compounds.
The benzofuran skeleton widely exists in natural products and synthetic medicines. Many benzofuran derivatives have important physiological, pharmacological and toxicological activities, and their synthesis methods have attracted much attention. A method of "one pot" synthesis ethyl benzofuran-3-carboxylate was obtained:in the presence of Et3N, toluene was used as a solvent, the mole ratio of o-iodophenol to ethyl propiolate was 1:1.5, and the reaction was carried out at room temperature for 20 min; then adding K2CO3, Pd(OAc)2/PPh3 85℃ for 3.5h, the product yield reached 78%. By improving the synthesis method, the process avoids the use of highly toxic diazo compound, and has the advantages of less steps, short time, simple operation and high yield. The method reported in this paper has implications for the synthesis of similar compounds.
