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2019 Volume 82 Issue 2
2019, 82(2): 99-107
Abstract:
Metal-organic frameworks (MOFs), also called porous coordination polymers (PCPs), are a class of crystalline porous materials built from organic linkers and metal ions/clusters. The unique features of MOFs, including high surface area, uniform channels, thermal stability and tailorability enable them have great potential applications in many fields. As the subfield of MOF-based sensing has developed, MOFs with fluorometric sensing properties have been developed by introducing many diverse chemical functionalties. This paper summarizes the topical developments in a number of crucial sensing domains, including ionic species, pH, volatile organic compounds and gas, explosives, biomolecules, and many others, also prospect the development trend of MOFs in chemical sensors.
Metal-organic frameworks (MOFs), also called porous coordination polymers (PCPs), are a class of crystalline porous materials built from organic linkers and metal ions/clusters. The unique features of MOFs, including high surface area, uniform channels, thermal stability and tailorability enable them have great potential applications in many fields. As the subfield of MOF-based sensing has developed, MOFs with fluorometric sensing properties have been developed by introducing many diverse chemical functionalties. This paper summarizes the topical developments in a number of crucial sensing domains, including ionic species, pH, volatile organic compounds and gas, explosives, biomolecules, and many others, also prospect the development trend of MOFs in chemical sensors.
2019, 82(2): 108-113
Abstract:
In the past decade, porous coordination polymers (PCPs) have attracted significant attention in the area of selective adsorption & separation of small molecules due to their unique crystal structure with the tunable pore size, pore shape and chemical functionalization. Environmental problems are becoming more and more serious. The excellent selective adsorption performance of amine functionalized PCPs on CO2 makes it have good application potential in treatment of carbon dioxide from flue gas. This paper reviews the representative work of PCPs containing terminal amino ligands for CO2 capture and storage, and analyzes the problems and development directions.
In the past decade, porous coordination polymers (PCPs) have attracted significant attention in the area of selective adsorption & separation of small molecules due to their unique crystal structure with the tunable pore size, pore shape and chemical functionalization. Environmental problems are becoming more and more serious. The excellent selective adsorption performance of amine functionalized PCPs on CO2 makes it have good application potential in treatment of carbon dioxide from flue gas. This paper reviews the representative work of PCPs containing terminal amino ligands for CO2 capture and storage, and analyzes the problems and development directions.
2019, 82(2): 114-119
Abstract:
The difunctionalization of alkynes has attracted considerable attention in recent years. This simple, highly efficient, atomic economy strategy could introduce different functional groups in one step. Many studies on copper-catalyzed difunctionalization of alkynes reaction were developed recently. In this paper, we summarize the recent progress in copper-catalyzed difunctionalization of alkynes.
The difunctionalization of alkynes has attracted considerable attention in recent years. This simple, highly efficient, atomic economy strategy could introduce different functional groups in one step. Many studies on copper-catalyzed difunctionalization of alkynes reaction were developed recently. In this paper, we summarize the recent progress in copper-catalyzed difunctionalization of alkynes.
2019, 82(2): 120-127
Abstract:
s-Triazolothiadiazoles compounds are a kind of important fused heterocyclic compounds, which have extensive biological activity such as anti-bacterial, anti-inflammatory, anti-tumor, anti-tuberculosis, enzyme inhibition, regulating plant growth activity and so on. According to the different biological activities of s-triazolothiadiazoles compounds, the research progress of biological activities for the titled compounds in recent years are reviewed.
s-Triazolothiadiazoles compounds are a kind of important fused heterocyclic compounds, which have extensive biological activity such as anti-bacterial, anti-inflammatory, anti-tumor, anti-tuberculosis, enzyme inhibition, regulating plant growth activity and so on. According to the different biological activities of s-triazolothiadiazoles compounds, the research progress of biological activities for the titled compounds in recent years are reviewed.
2019, 82(2): 128-132
Abstract:
In order to improve the antiplatelet agglutination activity of ligustrazine, different diamines, 2, 3-butanedione and lipoic acid were used as starting materials, seven ligustrazine derivatives were synthesized via four routes, including bromination, hydrolysis, cyclization, oxidation, hydrogenation and substitution reaction. Their structures were confirmed by 1H NMR, 13C NMR and ESI-MS, and the in vitro anti-platelet aggregation activities were tested preliminarily by the Born turbidimetric method. The experimental results showed that compounds 1 (IC50=0.26 mmol/L), 2 (IC50=0.27 mmol/L) and 7 (IC50=0.21 mmol/L) exhibit significant inhibitory activity for adenosine diphosphate (ADP) induced platelet aggregation, which are superior to the lead compound ligustrazine (IC50=0.49 mmol/L). Therefore, without changing ligustrazine pharmacophore, cyclization in different degree can obviously improve the antiplatelet agglutination activity of ligustrazine, which has useful reference value for the structure modification of lead compound.
In order to improve the antiplatelet agglutination activity of ligustrazine, different diamines, 2, 3-butanedione and lipoic acid were used as starting materials, seven ligustrazine derivatives were synthesized via four routes, including bromination, hydrolysis, cyclization, oxidation, hydrogenation and substitution reaction. Their structures were confirmed by 1H NMR, 13C NMR and ESI-MS, and the in vitro anti-platelet aggregation activities were tested preliminarily by the Born turbidimetric method. The experimental results showed that compounds 1 (IC50=0.26 mmol/L), 2 (IC50=0.27 mmol/L) and 7 (IC50=0.21 mmol/L) exhibit significant inhibitory activity for adenosine diphosphate (ADP) induced platelet aggregation, which are superior to the lead compound ligustrazine (IC50=0.49 mmol/L). Therefore, without changing ligustrazine pharmacophore, cyclization in different degree can obviously improve the antiplatelet agglutination activity of ligustrazine, which has useful reference value for the structure modification of lead compound.
2019, 82(2): 133-137
Abstract:
Formoterol fumarate is widely used as a therapeutic agent in the treatment of asthma. In this work, the synthesis process for preparation of formoterol fumarate was optimized and improved. 4-Benzyloxy-3-nitrophenyloxirane (Intermediate 3), one of the important intermediates, was obtained from 4-hydroxy-3-nitroacetophenone by benzylation, bromination, reduction and epoxidation reactions. During the preparing of intermediate 3, a one-pot method was adopted to simplify the processing. Potassium carbonate as an acid-binding agent was added in the reaction to accelerate the reaction rate and increase the yield. Another important intermediate, 1-(4-methoxyphenyl-2-methylethyl)benzylamine (Intermediate 4) was prepared from p-methoxyphenylacetone by a one-step reductive amination reaction. 3 and 4 were coupled to obtain intermediate 5 under microwave condition in a considerably short period. After nitro reduction, formylation, deprotection and salification, formoterol fumarate was obtained. This optimized method is simple and suitable for industrial production of formoterol fumarate with total yield of 7.46%.
Formoterol fumarate is widely used as a therapeutic agent in the treatment of asthma. In this work, the synthesis process for preparation of formoterol fumarate was optimized and improved. 4-Benzyloxy-3-nitrophenyloxirane (Intermediate 3), one of the important intermediates, was obtained from 4-hydroxy-3-nitroacetophenone by benzylation, bromination, reduction and epoxidation reactions. During the preparing of intermediate 3, a one-pot method was adopted to simplify the processing. Potassium carbonate as an acid-binding agent was added in the reaction to accelerate the reaction rate and increase the yield. Another important intermediate, 1-(4-methoxyphenyl-2-methylethyl)benzylamine (Intermediate 4) was prepared from p-methoxyphenylacetone by a one-step reductive amination reaction. 3 and 4 were coupled to obtain intermediate 5 under microwave condition in a considerably short period. After nitro reduction, formylation, deprotection and salification, formoterol fumarate was obtained. This optimized method is simple and suitable for industrial production of formoterol fumarate with total yield of 7.46%.
2019, 82(2): 138-143
Abstract:
A novel dendritic pyridineimine ligand DPI was synthesized using 1.0G dendritic polyamide-amine and pyridine dialdehyde as the raw materials, and the dendritic pyridineimine chromium (DPI-Cr) catalyst was synthesized with chromium chloride hexahydrate complex as reagent. The structure of the DPI-Cr catalyst was fully characterized by FT-IR, UV-Vis, MS and element analysis. The effect of solvent type, co-catalyst type, reaction temperature, reaction pressure and Al/Cr molar ratio on the catalytic performance in ethylene oligomerization was detected in detail. The results showed that the DPI-Cr catalyst displays better catalytic activity and olefine selectivity. Under the optimal reaction conditions, the catalytic activity could reach up to 4.91×104 g/(molCr·h), and the selectivity of C6 and C8 was 73.90%.
A novel dendritic pyridineimine ligand DPI was synthesized using 1.0G dendritic polyamide-amine and pyridine dialdehyde as the raw materials, and the dendritic pyridineimine chromium (DPI-Cr) catalyst was synthesized with chromium chloride hexahydrate complex as reagent. The structure of the DPI-Cr catalyst was fully characterized by FT-IR, UV-Vis, MS and element analysis. The effect of solvent type, co-catalyst type, reaction temperature, reaction pressure and Al/Cr molar ratio on the catalytic performance in ethylene oligomerization was detected in detail. The results showed that the DPI-Cr catalyst displays better catalytic activity and olefine selectivity. Under the optimal reaction conditions, the catalytic activity could reach up to 4.91×104 g/(molCr·h), and the selectivity of C6 and C8 was 73.90%.
2019, 82(2): 144-150
Abstract:
NH2-functionalized ferromanganese nanoparticles (AMFNs) was synthesized by one-step hydrothermal method, and its adsorption characteristics and adsorption capacities for Pb2+ and Cd2+ were also investigated. The AMFNs material characterization was characterized by SEM, FTIR, XPS and XRD etc. The maximum saturated adsorptions on AMFNs achieve 255.57 mg/g and 129.72 mg/g for Pb2+ and Cd2+ at the reaction time 60 min and the temperature 25℃ respectively. The adsorption kinetic and adsorption isotherm are conformed to the pseudo-second-order kinetic and Langmuir isotherm models, respectively. These results showed that the monomolecular chemisorption plays a dominant role in Pb2+ and Cd2+ adsorption process. In addition, desorption experiments indicated that the removal efficiency of AMFNs to Pb2+ and Cd2+ can still up to 87% after five repetition tests, which shows a good regenerative adsorption performance.
NH2-functionalized ferromanganese nanoparticles (AMFNs) was synthesized by one-step hydrothermal method, and its adsorption characteristics and adsorption capacities for Pb2+ and Cd2+ were also investigated. The AMFNs material characterization was characterized by SEM, FTIR, XPS and XRD etc. The maximum saturated adsorptions on AMFNs achieve 255.57 mg/g and 129.72 mg/g for Pb2+ and Cd2+ at the reaction time 60 min and the temperature 25℃ respectively. The adsorption kinetic and adsorption isotherm are conformed to the pseudo-second-order kinetic and Langmuir isotherm models, respectively. These results showed that the monomolecular chemisorption plays a dominant role in Pb2+ and Cd2+ adsorption process. In addition, desorption experiments indicated that the removal efficiency of AMFNs to Pb2+ and Cd2+ can still up to 87% after five repetition tests, which shows a good regenerative adsorption performance.
2019, 82(2): 151-157
Abstract:
Reasonable determination and regional division of supercritical water in critical regions plays an important role in understanding the characteristics of supercritical water flow and heat exchange in critical transition regions. In this paper, the transition characteristics of supercritical water from the quasi-liquid state to the quasi-vapor state are analyzed, and the characteristics of the variation of the thermal conductivity, dynamic viscosity, constant pressure ratio and expansion coefficient are also discussed. The classification and decision model of supercritical water in critical region are summarized. The results showed that the flow characteristic parameters and heat exchange characteristic parameters of supercritical water have a series of continuous and drastic changes in the critical transition zone of supercritical water. The critical region of supercritical water can be divided more reasonably by considering the expansion property of supercritical water and the maximum specific heat characteristic. On the basis of this analysis, the three-zone analysis decision model of supercritical water is improved, and the data of the new supercritical water in the critical region are obtained. The boundary calculation equation of the new supercritical water area is obtained. It has an error range of ±0.3℃, meeting the requirements of the calculation and analysis.
Reasonable determination and regional division of supercritical water in critical regions plays an important role in understanding the characteristics of supercritical water flow and heat exchange in critical transition regions. In this paper, the transition characteristics of supercritical water from the quasi-liquid state to the quasi-vapor state are analyzed, and the characteristics of the variation of the thermal conductivity, dynamic viscosity, constant pressure ratio and expansion coefficient are also discussed. The classification and decision model of supercritical water in critical region are summarized. The results showed that the flow characteristic parameters and heat exchange characteristic parameters of supercritical water have a series of continuous and drastic changes in the critical transition zone of supercritical water. The critical region of supercritical water can be divided more reasonably by considering the expansion property of supercritical water and the maximum specific heat characteristic. On the basis of this analysis, the three-zone analysis decision model of supercritical water is improved, and the data of the new supercritical water in the critical region are obtained. The boundary calculation equation of the new supercritical water area is obtained. It has an error range of ±0.3℃, meeting the requirements of the calculation and analysis.
2019, 82(2): 158-162
Abstract:
The thermal decomposition for n-octane, n-nonane, n-decane, n-undecane, and n-dodecane under supercritical condition is investigated in a constant-volume reactor respectively. A simplifying assumption of the first-order reaction is used to describe the decomposition of the n-alkanes. The gaseous and liquid products of the thermal decomposition are monitored, and the relationship between the amounts of produced aromatics in the liquid residues and their thermal stability is investigated. At the same conditions of reaction temperature and time, the rate of thermal decomposition, the conversion, or the content of aromatic products increases with increasing the number of odd or even carbon atoms of alkanes, respectively. The produced aromatics increases exponentially with increasing the conversion of thermal decomposition, which reflects the regular changes of the thermal stability and decomposition severity of hydrocarbon fuels.
The thermal decomposition for n-octane, n-nonane, n-decane, n-undecane, and n-dodecane under supercritical condition is investigated in a constant-volume reactor respectively. A simplifying assumption of the first-order reaction is used to describe the decomposition of the n-alkanes. The gaseous and liquid products of the thermal decomposition are monitored, and the relationship between the amounts of produced aromatics in the liquid residues and their thermal stability is investigated. At the same conditions of reaction temperature and time, the rate of thermal decomposition, the conversion, or the content of aromatic products increases with increasing the number of odd or even carbon atoms of alkanes, respectively. The produced aromatics increases exponentially with increasing the conversion of thermal decomposition, which reflects the regular changes of the thermal stability and decomposition severity of hydrocarbon fuels.
2019, 82(2): 163-168
Abstract:
High fluoride groundwater de-fluorination is one of the most effective methods to ensure local residents away from endemically fluorine diseases. A new type of sealing de-fluorination device was used to find out the driving force, influence factors and de-fluorination ability of dynamic de-fluorination with limestone in electric field. The results showed that the fluorine could be degraded and the fluorite would be over formed as the reacting between limestone and high fluoride water in electric field. The whole process could be divided into initialization phase and stabilization phase. Furthermore, the voltage gradient is the main factor of the de-fluorination. The ability of de-fluorination would increase if the voltage gradient is over 4.8V/cm. During the process, the concentration of F- would enrich at anode and CaF2 would be formatted at cathode, which indicate de-fluorination will be better at cathode. Also, the configuration of limestone surface varied much and corrosion could be observed clearly. When the voltage was 24 V and distance between electrodes was 3cm, the concentration of fluoride at cathode decreased to the nation sanitary standard for drinking water quickly.
High fluoride groundwater de-fluorination is one of the most effective methods to ensure local residents away from endemically fluorine diseases. A new type of sealing de-fluorination device was used to find out the driving force, influence factors and de-fluorination ability of dynamic de-fluorination with limestone in electric field. The results showed that the fluorine could be degraded and the fluorite would be over formed as the reacting between limestone and high fluoride water in electric field. The whole process could be divided into initialization phase and stabilization phase. Furthermore, the voltage gradient is the main factor of the de-fluorination. The ability of de-fluorination would increase if the voltage gradient is over 4.8V/cm. During the process, the concentration of F- would enrich at anode and CaF2 would be formatted at cathode, which indicate de-fluorination will be better at cathode. Also, the configuration of limestone surface varied much and corrosion could be observed clearly. When the voltage was 24 V and distance between electrodes was 3cm, the concentration of fluoride at cathode decreased to the nation sanitary standard for drinking water quickly.
2019, 82(2): 169-174
Abstract:
It's especially important for identifying the marker pens ink in the detection and litigation of related cases. This paper acquired the original spectra of the marker pens ink by ATR-FTIR, and used automatic baseline correction, Savitzky-Golay smoothing, peak area normalization and wavelet threshold denoising to eliminate interference factors, determine the characteristic wavelength range and pretreat the original spectrum. Simultaneously, the paper combined with discriminant analysis (DA), radial basis function neural network (RBF) and K nearest neighbor algorithm (KNN) to construct multi-classification model. The results showed that the three models have the most accurate classification of black pens and achieve 100% recognition, followed by the the red and blue pens. Compared with DA and RBF, KNN model has the highest classification accuracy. Using ATR-FTIR combined with DA-RBF-KNN can provide a new analysis method for more accurate detection of marker pens ink. The method has certain universality and reference significance.
It's especially important for identifying the marker pens ink in the detection and litigation of related cases. This paper acquired the original spectra of the marker pens ink by ATR-FTIR, and used automatic baseline correction, Savitzky-Golay smoothing, peak area normalization and wavelet threshold denoising to eliminate interference factors, determine the characteristic wavelength range and pretreat the original spectrum. Simultaneously, the paper combined with discriminant analysis (DA), radial basis function neural network (RBF) and K nearest neighbor algorithm (KNN) to construct multi-classification model. The results showed that the three models have the most accurate classification of black pens and achieve 100% recognition, followed by the the red and blue pens. Compared with DA and RBF, KNN model has the highest classification accuracy. Using ATR-FTIR combined with DA-RBF-KNN can provide a new analysis method for more accurate detection of marker pens ink. The method has certain universality and reference significance.
2019, 82(2): 175-178
Abstract:
The biomimetic mesoporous silica is a mesoporous silica, which using organic silicane as a template that can effectively reproduce the unique morphology of the template, thereby obtaining the same or similar mesoporous structure with mesoporous silica. In this paper, bionic mesoporous silica was prepared from the biomimetic point of view, and the bionic chiral nematic mesoporous silica was prepared by extracted the chitin film from the crab shell as a template, and then the bionic chiral nematic mesoporous silica was used to prepare liquid chromatography column. The prepared column was used for the separation of chiral compounds in the high performance liquid chromatograph. The experimental results showed that the chromatographic stationary phase has a certain chiral separation effect to 10 chiral compounds.
The biomimetic mesoporous silica is a mesoporous silica, which using organic silicane as a template that can effectively reproduce the unique morphology of the template, thereby obtaining the same or similar mesoporous structure with mesoporous silica. In this paper, bionic mesoporous silica was prepared from the biomimetic point of view, and the bionic chiral nematic mesoporous silica was prepared by extracted the chitin film from the crab shell as a template, and then the bionic chiral nematic mesoporous silica was used to prepare liquid chromatography column. The prepared column was used for the separation of chiral compounds in the high performance liquid chromatograph. The experimental results showed that the chromatographic stationary phase has a certain chiral separation effect to 10 chiral compounds.
2019, 82(2): 179-182
Abstract:
The studies on fluorescence titration of Tb(Ⅲ) to N, N-bis(carboxylphenyl)-2, 6-pyridinedicarboxamide (BCPD) showed that there are two coordination modes of Tb(Ⅲ) with BCPD:(BCPD)2Tb and (BCPD)Tb. The further study on emission fluorescence of BCPD and time scan intrinsic fluorescence of Tb(Ⅲ) proved that the two coordination modes were existed during the titration of Tb(Ⅲ) to BCPD. The results enriches the coordination theory and contributes to the preparation of fluorescent materials.
The studies on fluorescence titration of Tb(Ⅲ) to N, N-bis(carboxylphenyl)-2, 6-pyridinedicarboxamide (BCPD) showed that there are two coordination modes of Tb(Ⅲ) with BCPD:(BCPD)2Tb and (BCPD)Tb. The further study on emission fluorescence of BCPD and time scan intrinsic fluorescence of Tb(Ⅲ) proved that the two coordination modes were existed during the titration of Tb(Ⅲ) to BCPD. The results enriches the coordination theory and contributes to the preparation of fluorescent materials.
2019, 82(2): 183-186
Abstract:
DSPE was synthesized by reactions with glycerol-1, 2-distearate, phosphorusoxychloride and 2-aminoethanol as raw materials. N3-PEG2000 was achieved by an efficient two step process from readily available PEG2000. Subsequently, N3-PEG2000-DSPE was obtained by linking DSPE to N3-PEG2000 via CDI. Finally, catalytic hydrogenation of the azido group yielded the target compound NH2-PEG2000-DSPE, which was characterized by IR, 1H NMR, and MS.
DSPE was synthesized by reactions with glycerol-1, 2-distearate, phosphorusoxychloride and 2-aminoethanol as raw materials. N3-PEG2000 was achieved by an efficient two step process from readily available PEG2000. Subsequently, N3-PEG2000-DSPE was obtained by linking DSPE to N3-PEG2000 via CDI. Finally, catalytic hydrogenation of the azido group yielded the target compound NH2-PEG2000-DSPE, which was characterized by IR, 1H NMR, and MS.
2019, 82(2): 187-191
Abstract:
The research of Au nanoparticles (AuNPs) appears to be one of the most popular subjects over the past decade. AuNPs are synthesized controllably at a mild condition and this process only involves two reactants, chloroauric acid and boron clusters, in which Cs2[closo-B12H12], a cesium boron cluster, can play a dual role as reductant and stabilizer. The obtained AuNPs remained thermodynamically stable over 3 months, and exhibited high performance in phase transfer and sensing of heavy metal ions. The results can be used as a comprehensive experiment in the course of analysis chemistry experiment. The students can learn how to use UV-Vis and other methods to characterize the nanoparticles.
The research of Au nanoparticles (AuNPs) appears to be one of the most popular subjects over the past decade. AuNPs are synthesized controllably at a mild condition and this process only involves two reactants, chloroauric acid and boron clusters, in which Cs2[closo-B12H12], a cesium boron cluster, can play a dual role as reductant and stabilizer. The obtained AuNPs remained thermodynamically stable over 3 months, and exhibited high performance in phase transfer and sensing of heavy metal ions. The results can be used as a comprehensive experiment in the course of analysis chemistry experiment. The students can learn how to use UV-Vis and other methods to characterize the nanoparticles.
