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2019 Volume 82 Issue 9
2019, 82(9): 771-778
Abstract:
Accurate and quantitative detection of Fe3+ is of great significance to environmental protection and human health. At present, a large number of fluorescent sensing materials were developed for the detection in molecular sensing, gas sensing, environment monitoring and other areas. Researchers have vigorously developed a variety of novel fluorescent materials to achieve fast, ultra-sensitive and ultra-selective detection of Fe3+. In this paper, recent advances in advanced fluorescent materials for the detection of Fe3+, particularly, metal-organic frameworks (MOFs), quantum dots (QDs), metal nanoclusters, fluorescent small molecules, fluorescent polymers are summarized. Subsequently, the problems and the limitations in fluorescent sensing materials are briefly discussed, and the developing orientation for further research is also pointed out.
Accurate and quantitative detection of Fe3+ is of great significance to environmental protection and human health. At present, a large number of fluorescent sensing materials were developed for the detection in molecular sensing, gas sensing, environment monitoring and other areas. Researchers have vigorously developed a variety of novel fluorescent materials to achieve fast, ultra-sensitive and ultra-selective detection of Fe3+. In this paper, recent advances in advanced fluorescent materials for the detection of Fe3+, particularly, metal-organic frameworks (MOFs), quantum dots (QDs), metal nanoclusters, fluorescent small molecules, fluorescent polymers are summarized. Subsequently, the problems and the limitations in fluorescent sensing materials are briefly discussed, and the developing orientation for further research is also pointed out.
2019, 82(9): 779-788
Abstract:
Quinazoline and its derivatives, as an important pharmacophore, have a broad spectrum of antitumor biological activity, and have been the focus of medicinal chemistry research. In this paper, the syntheses of quinazoline derivatives with different substituents such as amides, halogens, ethers, 7-rings, heterocyclics derivatives, as well as their antitumor biological activity were reviewed. It is expected to provide a reference for the desigs and syntheses of new anticancer compounds with higher activity and less toxicity.
Quinazoline and its derivatives, as an important pharmacophore, have a broad spectrum of antitumor biological activity, and have been the focus of medicinal chemistry research. In this paper, the syntheses of quinazoline derivatives with different substituents such as amides, halogens, ethers, 7-rings, heterocyclics derivatives, as well as their antitumor biological activity were reviewed. It is expected to provide a reference for the desigs and syntheses of new anticancer compounds with higher activity and less toxicity.
2019, 82(9): 789-795
Abstract:
Coumarin and its derivatives are a key class of heterocyclic lactone compounds, which are widely applied in the fields of organic synthesis, pharmaceutics, fluorescent materials, and so on. The development of a novel simple and efficient synthetic strategy of coumarins has been paid much attention. Recently, the tandem radical addition/cyclization of alkynoate with radical precursor afforded a simple, green and efficient method to synthesize coumarins. In this review, the recent progress in the synthesis of coumarins through tandem radical addition/cyclization is summarized.
Coumarin and its derivatives are a key class of heterocyclic lactone compounds, which are widely applied in the fields of organic synthesis, pharmaceutics, fluorescent materials, and so on. The development of a novel simple and efficient synthetic strategy of coumarins has been paid much attention. Recently, the tandem radical addition/cyclization of alkynoate with radical precursor afforded a simple, green and efficient method to synthesize coumarins. In this review, the recent progress in the synthesis of coumarins through tandem radical addition/cyclization is summarized.
2019, 82(9): 796-800
Abstract:
MOFs is a kind of material with highly ordered pore structure and large specific surface area, MOFs containing BODIPY chromophore are materials prepared by designing BODIPY chromophore as a ligand that can coordinate with metal centers and directly coordinate with metal ions, or introducing the chromophore into MOFs materials as an optical absorption antenna. Such materials have been widely concerned for their strong absorption of visible light. In this paper, the preparation methods of MOFs containing BODIPY chromophore were summarized. The structure characteristics, photophysical properties and application prospect of this kind of materials were discussed. Finally, the prospect and development trend of this kind of materials in the future are prospected. This paper can provide reference for the development of such materials in the field of photochemistry.
MOFs is a kind of material with highly ordered pore structure and large specific surface area, MOFs containing BODIPY chromophore are materials prepared by designing BODIPY chromophore as a ligand that can coordinate with metal centers and directly coordinate with metal ions, or introducing the chromophore into MOFs materials as an optical absorption antenna. Such materials have been widely concerned for their strong absorption of visible light. In this paper, the preparation methods of MOFs containing BODIPY chromophore were summarized. The structure characteristics, photophysical properties and application prospect of this kind of materials were discussed. Finally, the prospect and development trend of this kind of materials in the future are prospected. This paper can provide reference for the development of such materials in the field of photochemistry.
2019, 82(9): 801-805
Abstract:
Chloropropanol esters and glycidyl esters are potentially harmful to humans and have been found widely in refined vegetable oils and oily foods. This problem has caused widespread concern in the industry, and the related research on this issue is constantly deepening. However, there are still many problems that need to be solved. This paper reviews the sources, formation mechanism and toxicity of chloropropanol esters and glycidyl esters in foods. In addition, the research status of the relevant regulations and detection methods for chloropropanol esters and glycidyl esters in foods at home and abroad are introduced in detail.
Chloropropanol esters and glycidyl esters are potentially harmful to humans and have been found widely in refined vegetable oils and oily foods. This problem has caused widespread concern in the industry, and the related research on this issue is constantly deepening. However, there are still many problems that need to be solved. This paper reviews the sources, formation mechanism and toxicity of chloropropanol esters and glycidyl esters in foods. In addition, the research status of the relevant regulations and detection methods for chloropropanol esters and glycidyl esters in foods at home and abroad are introduced in detail.
2019, 82(9): 806-810
Abstract:
A series of LaNi1-xCoxO3 (x=0, 0.2, 0.4, 0.6, 0.8, 1.0) catalysts were prepared by co-precipitation method. The influence of doping of B-site Co ions on LaNiO3 catalyst performance was investigated. The catalyst samples were characterized by XRD, BET, H2-TPR, SEM and TG-DSC techniques. Their catalytic activities were evaluated for methane catalytic combustion. The results showed that the doping of Co ions would result in the change of crystal structure and improvement of the catalytic activity. The catalyst LaNi0.2Co0.8O3 retained a specific surface area of 22.4 m2·g-1 and showed excellent activity for methane combustion. The temperature at conversion of 10% and 90% were 475℃ and 610℃, respectively.
A series of LaNi1-xCoxO3 (x=0, 0.2, 0.4, 0.6, 0.8, 1.0) catalysts were prepared by co-precipitation method. The influence of doping of B-site Co ions on LaNiO3 catalyst performance was investigated. The catalyst samples were characterized by XRD, BET, H2-TPR, SEM and TG-DSC techniques. Their catalytic activities were evaluated for methane catalytic combustion. The results showed that the doping of Co ions would result in the change of crystal structure and improvement of the catalytic activity. The catalyst LaNi0.2Co0.8O3 retained a specific surface area of 22.4 m2·g-1 and showed excellent activity for methane combustion. The temperature at conversion of 10% and 90% were 475℃ and 610℃, respectively.
2019, 82(9): 811-815
Abstract:
An amino-functionalized As(Ⅴ)-ion imprinted organic-inorganic hybrid sorbent was prepared by hydrothermal assisted surface imprinting technique, and then its morphology and functional groups were characterized by SEM and FTIR. The adsorption property and selective removal ability of the imprinted hybrid sorbent were investigated by batch method. The results showed that the static adsorption capacity of the imprinted hybrid sorbent was improved evidently. At 20℃, the adsorption amount reached 47.5 mg/g, and the adsorption equilibrium time was 30 min. There was insignificant effect of pH in the range of 4~9 on the adsorption capacity of As(Ⅴ). The imprinted hybrid sorbent showed good selectivity for As(Ⅴ) in the binary solution. After the imprinted hybrid sorbent was reused 5 cycles, no substantial reduction of adsorption capacity was observed. The adsorption process of As(Ⅴ) onto the imprinted hybrid sorbent followed Langmuir isotherm and pseudo-second order kinetic model.
An amino-functionalized As(Ⅴ)-ion imprinted organic-inorganic hybrid sorbent was prepared by hydrothermal assisted surface imprinting technique, and then its morphology and functional groups were characterized by SEM and FTIR. The adsorption property and selective removal ability of the imprinted hybrid sorbent were investigated by batch method. The results showed that the static adsorption capacity of the imprinted hybrid sorbent was improved evidently. At 20℃, the adsorption amount reached 47.5 mg/g, and the adsorption equilibrium time was 30 min. There was insignificant effect of pH in the range of 4~9 on the adsorption capacity of As(Ⅴ). The imprinted hybrid sorbent showed good selectivity for As(Ⅴ) in the binary solution. After the imprinted hybrid sorbent was reused 5 cycles, no substantial reduction of adsorption capacity was observed. The adsorption process of As(Ⅴ) onto the imprinted hybrid sorbent followed Langmuir isotherm and pseudo-second order kinetic model.
2019, 82(9): 816-820
Abstract:
The monodisperse oil-in-water (O/W) emulsions were prepared by using a glass capillary tube to build a single-stage microfluidic device. The Poly (methyl methacrylate/dimethylaminoethyl methacrylate)[P(MMA/DMAEMA)] porous microspheres were successfully prepared by free radical polymerization under UV irradiation using the emulsion as a template. The particle deviation coefficient (CV) value of the microspheres was less than 5%, indicating the good monodispersity. The adsorption mechanism, regenerative adsorption property and adsorption property of prepared porous microspheres for Cr(VI) were investigated. The results showed that the pH have a great influence on the adsorption rate of microspheres. The microsphere adsorption conforms to the quasi-secondary kinetic model and belongs to the chemical adsorption. Meanwhile, the microsphere isotherm adsorption conforms to the Langmuir model and belongs to the monolayer adsorption.
The monodisperse oil-in-water (O/W) emulsions were prepared by using a glass capillary tube to build a single-stage microfluidic device. The Poly (methyl methacrylate/dimethylaminoethyl methacrylate)[P(MMA/DMAEMA)] porous microspheres were successfully prepared by free radical polymerization under UV irradiation using the emulsion as a template. The particle deviation coefficient (CV) value of the microspheres was less than 5%, indicating the good monodispersity. The adsorption mechanism, regenerative adsorption property and adsorption property of prepared porous microspheres for Cr(VI) were investigated. The results showed that the pH have a great influence on the adsorption rate of microspheres. The microsphere adsorption conforms to the quasi-secondary kinetic model and belongs to the chemical adsorption. Meanwhile, the microsphere isotherm adsorption conforms to the Langmuir model and belongs to the monolayer adsorption.
2019, 82(9): 821-825
Abstract:
Three kinds of methyl N-substituted-5-oxopyrrolidine-3-carboxylate (2a~2c) were synthesized by a Michael addition reaction of dimethyl itaconate and three types of alcyl amines respectively, and they were further hydrolyzed under basic conditions to afford three N-substituted-5-oxopyrrolidine-3-carboxylic acids (1a~1c). The structure of the products and intermediates were confirmed by 1H NMR, 13C NMR and ESI-MS. Taking the Michael addition reaction of dimethyl itaconate and cyclobutylamine as a model, the optimized reaction process of this step was finally determined as follows:n(cyclobutanamine):n(dimethyl itaconate)=1.3:1, reacting in toluene at 110℃ for 2 h. Compound 2b was obtained in a yield of 91.2%, and its structure was further confirmed by X-ray single crystal diffraction.
Three kinds of methyl N-substituted-5-oxopyrrolidine-3-carboxylate (2a~2c) were synthesized by a Michael addition reaction of dimethyl itaconate and three types of alcyl amines respectively, and they were further hydrolyzed under basic conditions to afford three N-substituted-5-oxopyrrolidine-3-carboxylic acids (1a~1c). The structure of the products and intermediates were confirmed by 1H NMR, 13C NMR and ESI-MS. Taking the Michael addition reaction of dimethyl itaconate and cyclobutylamine as a model, the optimized reaction process of this step was finally determined as follows:n(cyclobutanamine):n(dimethyl itaconate)=1.3:1, reacting in toluene at 110℃ for 2 h. Compound 2b was obtained in a yield of 91.2%, and its structure was further confirmed by X-ray single crystal diffraction.
2019, 82(9): 826-830
Abstract:
The synthetic process of saflufenacil and its key intermediates is designed and completed, which has the potential for industrial manufacturing. The key intermediate N-methyl-N-isopropylaminosulfonamide is prepared by using chlorosulfonyl isocyanate, t-butanol, N-methyl-N-isopropylamine as the starting material. The overall yield of the three-step reaction is about 75%. Then, 2-chloro-4-fluorobenzoic acid was used as a raw material to prepare saflufenacil by nitration, chloridization, condensation, catalytic hydrogenation reduction, aminolysis and methylation reactions. The total yield of 8 steps is 48.6%, and the purity of the target product is 98.6%. The final products and the intermediates are characterized by NMR and MS.
The synthetic process of saflufenacil and its key intermediates is designed and completed, which has the potential for industrial manufacturing. The key intermediate N-methyl-N-isopropylaminosulfonamide is prepared by using chlorosulfonyl isocyanate, t-butanol, N-methyl-N-isopropylamine as the starting material. The overall yield of the three-step reaction is about 75%. Then, 2-chloro-4-fluorobenzoic acid was used as a raw material to prepare saflufenacil by nitration, chloridization, condensation, catalytic hydrogenation reduction, aminolysis and methylation reactions. The total yield of 8 steps is 48.6%, and the purity of the target product is 98.6%. The final products and the intermediates are characterized by NMR and MS.
2019, 82(9): 831-836, 854
Abstract:
In order to find triazole lead compounds with fungicidal activity, a series of new triazole derivatives containing coumarin ring and thioether structure were synthesized by the introduction of coumarin ring and thioether structural unit into molecules of triazoles. They were structurally confirmed by 1H NMR, 13C NMR, IR, MS and elemental analysis. The preliminary bioactivity test showed that some of the target compounds have certain fungicidal activity at the test concentration.
In order to find triazole lead compounds with fungicidal activity, a series of new triazole derivatives containing coumarin ring and thioether structure were synthesized by the introduction of coumarin ring and thioether structural unit into molecules of triazoles. They were structurally confirmed by 1H NMR, 13C NMR, IR, MS and elemental analysis. The preliminary bioactivity test showed that some of the target compounds have certain fungicidal activity at the test concentration.
2019, 82(9): 837-841
Abstract:
Avadomide is a potential drug for the treatment of advanced solid tumors, which is in phase Ⅱ clinical trials. In this work, the synthetic process of Avadomide was optimized and improved. Using 3-nitrophthalimide as the starting material, Avadomide was obtained by ring-cleavage, Hoffman degradation, cyclization, ester aminolysis reaction and Pd(OH)2/C hydrogenation reduction. The overall yield was 46.9%, and the target compound was identified by 1H NMR, 13C NMR and HRMS, whose purity was 99.5% through HPLC test. In comparison with literature methods, this synthetic route has the advantages of mild reaction conditions, simple post-treatment, high yield and easy work-up, so it is suitable for industrial production of Avadomide.
Avadomide is a potential drug for the treatment of advanced solid tumors, which is in phase Ⅱ clinical trials. In this work, the synthetic process of Avadomide was optimized and improved. Using 3-nitrophthalimide as the starting material, Avadomide was obtained by ring-cleavage, Hoffman degradation, cyclization, ester aminolysis reaction and Pd(OH)2/C hydrogenation reduction. The overall yield was 46.9%, and the target compound was identified by 1H NMR, 13C NMR and HRMS, whose purity was 99.5% through HPLC test. In comparison with literature methods, this synthetic route has the advantages of mild reaction conditions, simple post-treatment, high yield and easy work-up, so it is suitable for industrial production of Avadomide.
2019, 82(9): 842-848
Abstract:
The magnetic properties of the asymmetric dicopper (Ⅱ) complexes with mixed pyrazole/oxalato ligands were studied using DFT-BS by several DFT methods and basis sets. The calculated magnetic coupling constant Jcalc (-127.24 cm-1) under the B3LYP/def2-TZVP level is in agreement with the experimental parameter -129 cm-1, which can accurately describe the magnetic properties of the titled complexes. The analyses of magnetic orbitals and the spin density demonstrated that the spin delocalization is originated from Cu(Ⅱ) ion. Magnetic orbitals are mainly composed of 3dx2-y2 orbitals of Cu(Ⅱ) ions and π molecular orbital of the oxalato ion. As the structural parameter τ increase, the square deviations of the HS and BS state spin densities of the paramagnetic center, as well as the square of the overlap integrals between the natural magnetic orbitals are simultaneously ascended. As a result, the contribution of antiferromagnetic interaction is increased, whereas the magnitudes of the magnetic coupling constants are decreased.
The magnetic properties of the asymmetric dicopper (Ⅱ) complexes with mixed pyrazole/oxalato ligands were studied using DFT-BS by several DFT methods and basis sets. The calculated magnetic coupling constant Jcalc (-127.24 cm-1) under the B3LYP/def2-TZVP level is in agreement with the experimental parameter -129 cm-1, which can accurately describe the magnetic properties of the titled complexes. The analyses of magnetic orbitals and the spin density demonstrated that the spin delocalization is originated from Cu(Ⅱ) ion. Magnetic orbitals are mainly composed of 3dx2-y2 orbitals of Cu(Ⅱ) ions and π molecular orbital of the oxalato ion. As the structural parameter τ increase, the square deviations of the HS and BS state spin densities of the paramagnetic center, as well as the square of the overlap integrals between the natural magnetic orbitals are simultaneously ascended. As a result, the contribution of antiferromagnetic interaction is increased, whereas the magnitudes of the magnetic coupling constants are decreased.
2019, 82(9): 849-854
Abstract:
To solve the problems such as high pollution and high consumption existing in the traditional production technique of potassium dichromate, a new green technology of electrocatalytic synthesis of potassium dichromate was studied. Cyclic voltammetry has been used to investigate the electro-catalytic performance of anode, and the morphology and structure of anode were characterized by FESEM. The results indicated that the Ru/Ir/Ti oxide composite anode exhibits lower oxygen evolution potential in anolyte and stable high electrocatalytic activity. The hydrogen evolution rates of cathode at different reaction conditions were experimentally measured in the electrocatalysis synthesis process of potassium dichromate. The mathematical models were established for the dependence of hydrogen evolution rate and hydrogen evolution amount on initial potassium chromate concentration, reaction temperature, and reaction time. It was pointed out that the cathodic hydrogen evolution quantitatively measured may be used to characterize the electrocatalytic reaction process of potassium dichromate, and the influencing factors of hydrogen evolution rate and hydrogen evolution amount were discussed.
To solve the problems such as high pollution and high consumption existing in the traditional production technique of potassium dichromate, a new green technology of electrocatalytic synthesis of potassium dichromate was studied. Cyclic voltammetry has been used to investigate the electro-catalytic performance of anode, and the morphology and structure of anode were characterized by FESEM. The results indicated that the Ru/Ir/Ti oxide composite anode exhibits lower oxygen evolution potential in anolyte and stable high electrocatalytic activity. The hydrogen evolution rates of cathode at different reaction conditions were experimentally measured in the electrocatalysis synthesis process of potassium dichromate. The mathematical models were established for the dependence of hydrogen evolution rate and hydrogen evolution amount on initial potassium chromate concentration, reaction temperature, and reaction time. It was pointed out that the cathodic hydrogen evolution quantitatively measured may be used to characterize the electrocatalytic reaction process of potassium dichromate, and the influencing factors of hydrogen evolution rate and hydrogen evolution amount were discussed.
2019, 82(9): 855-859
Abstract:
Eight kinds of Mo8O26 based compounds were synthesized and the structure of these compounds were characterized by NMR and FT-IR. Microcrystalline cellulose (MCC) was hydrolyzed to produce the total reducing sugar (TRS) in ionic liquid[Amim]Cl using molybdenum polyoxometalate as catalyst under microwave irradiation conditions. The effects of the kind and dosage of catalyst, reaction temperature and reaction time on the hydrolysis reaction were investigated. The results indicated that the molybdenum polyoxometalates exhibit good catalytic activity for the hydrolysis reaction of MCC. The cellulose can be completely converted with the addition of 10(wt)% of catalyst[(CH3)4N]4Mo8O26 under the microwave-assisted heating condition in the ionic liquid[Amim]Cl at 170℃ for 20 min. The highest TRS and glucose yields of MCC were 84.5% and 41.5% respectively.
Eight kinds of Mo8O26 based compounds were synthesized and the structure of these compounds were characterized by NMR and FT-IR. Microcrystalline cellulose (MCC) was hydrolyzed to produce the total reducing sugar (TRS) in ionic liquid[Amim]Cl using molybdenum polyoxometalate as catalyst under microwave irradiation conditions. The effects of the kind and dosage of catalyst, reaction temperature and reaction time on the hydrolysis reaction were investigated. The results indicated that the molybdenum polyoxometalates exhibit good catalytic activity for the hydrolysis reaction of MCC. The cellulose can be completely converted with the addition of 10(wt)% of catalyst[(CH3)4N]4Mo8O26 under the microwave-assisted heating condition in the ionic liquid[Amim]Cl at 170℃ for 20 min. The highest TRS and glucose yields of MCC were 84.5% and 41.5% respectively.
2019, 82(9): 860-863
Abstract:
DNA-dependent protein kinase (DNA-PK) is a potential target for tumor therapy. DNA-PK inhibitor can enhance the sensitivities of tumor cells against chemotherapy and radiotherapy. STL127705 is an effective inhibitor of DNA-PK. By retrosynthetic analysis, using 4-chloro-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester as the starting material, the target compound was prepared by a six-step reaction including ammonification, hydrolysis, amide condensation, cyclization, oxidation and substitution, with an overall yield of 36.8%, the purity of target product reached 95.5% and the product structure was confirmed by 1H NMR, 13C NMR and MS.
DNA-dependent protein kinase (DNA-PK) is a potential target for tumor therapy. DNA-PK inhibitor can enhance the sensitivities of tumor cells against chemotherapy and radiotherapy. STL127705 is an effective inhibitor of DNA-PK. By retrosynthetic analysis, using 4-chloro-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester as the starting material, the target compound was prepared by a six-step reaction including ammonification, hydrolysis, amide condensation, cyclization, oxidation and substitution, with an overall yield of 36.8%, the purity of target product reached 95.5% and the product structure was confirmed by 1H NMR, 13C NMR and MS.
