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2017 Volume 34 Issue 6
2017, 34(6): 611-622
doi: 10.11944/j.issn.1000-0518.2017.06.160356
Abstract:
At present, malignant tumor has been becoming the main threat to human's death. Chemotherapy is one of the main methods of tumor therapy. However, there are many defects, such as side effects, drug resistance and difficulty of monitoring. Most of research works focus on improving the drugs' therapeutic effect and cutting down it's side effects, drugs' carriers are used to increase its concentration in the local lesions, which promote the efficiency of inhibiting tumor cells and reduce side effects with antitumor drugs. Perylenediimides derivatives(PDI) is a highly stable fluorescing materials, which is easily modified to enhance its biocompatibility and exercise a variety of functions. It can be used as drug carriers, fluorescence imaging, and anticancer drugs for cancers' diagnosis and treatment. This review focuses on the recent progress of PDI's biomedical applications and elaborates from drug carrier, antitumor drugs and fluorescent tracer aspects. This review summarized the basic experimental theory and gave the way for the application of PDI in clinical work.
At present, malignant tumor has been becoming the main threat to human's death. Chemotherapy is one of the main methods of tumor therapy. However, there are many defects, such as side effects, drug resistance and difficulty of monitoring. Most of research works focus on improving the drugs' therapeutic effect and cutting down it's side effects, drugs' carriers are used to increase its concentration in the local lesions, which promote the efficiency of inhibiting tumor cells and reduce side effects with antitumor drugs. Perylenediimides derivatives(PDI) is a highly stable fluorescing materials, which is easily modified to enhance its biocompatibility and exercise a variety of functions. It can be used as drug carriers, fluorescence imaging, and anticancer drugs for cancers' diagnosis and treatment. This review focuses on the recent progress of PDI's biomedical applications and elaborates from drug carrier, antitumor drugs and fluorescent tracer aspects. This review summarized the basic experimental theory and gave the way for the application of PDI in clinical work.
2017, 34(6): 623-630
doi: 10.11944/j.issn.1000-0518.2017.06.160381
Abstract:
A series of different content of benzimidazolone and 5, 6-dimethyl-2-benzimidazolone poly(aryl ether sulfone) copolymers with side groups were synthesized by copolymerization on the basis of poly(aryl ether sulfone) with cardo group(PES-C). The structures and properties of the copolymers were characterized by nuclear magnetic resonance spectroscopy(NMR), Fourier transform infrared spectrometer(FTIR), thermal gravimetric analyzer(TGA) and so on. The resulsts show that poly(aryl ether sulfone) copolymers are amorphous. The copolymers exhibit good heat resistance, and present a single glass transition temperature(Tg>271℃), when the mole fraction of benzimidazolone and 5, 6-dimethyl-2-benzimidazolone increases, the copolymer glass transition temperature rises, ranging from 270℃ to 318℃ and 314℃, respectively. At the same time, the copolymers have good thermal stability. These copolymers have good solubility in N, N-dimethyl formamide(DMF), N, N-dimethylacetamide(DMAc), dimethyl sulfoxide(DMSO), N-methyl pyrrolidone(NMP) which are the commonly polar aprotic solvents, and trichloromethane(CHCl3). Based on good solution processability and film-forming properties, the toughness thin film can be prepared by solution preparation.
A series of different content of benzimidazolone and 5, 6-dimethyl-2-benzimidazolone poly(aryl ether sulfone) copolymers with side groups were synthesized by copolymerization on the basis of poly(aryl ether sulfone) with cardo group(PES-C). The structures and properties of the copolymers were characterized by nuclear magnetic resonance spectroscopy(NMR), Fourier transform infrared spectrometer(FTIR), thermal gravimetric analyzer(TGA) and so on. The resulsts show that poly(aryl ether sulfone) copolymers are amorphous. The copolymers exhibit good heat resistance, and present a single glass transition temperature(Tg>271℃), when the mole fraction of benzimidazolone and 5, 6-dimethyl-2-benzimidazolone increases, the copolymer glass transition temperature rises, ranging from 270℃ to 318℃ and 314℃, respectively. At the same time, the copolymers have good thermal stability. These copolymers have good solubility in N, N-dimethyl formamide(DMF), N, N-dimethylacetamide(DMAc), dimethyl sulfoxide(DMSO), N-methyl pyrrolidone(NMP) which are the commonly polar aprotic solvents, and trichloromethane(CHCl3). Based on good solution processability and film-forming properties, the toughness thin film can be prepared by solution preparation.
2017, 34(6): 631-635
doi: 10.11944/j.issn.1000-0518.2017.06.160317
Abstract:
Phenolic resin(PF) is widely used due to its excellent heat resistance and mechanical properties. But its heat resistance cannot meet the demand of modern science and technology. Preparation of boron phenolic resin(BPF) with excellent high temperature resistance through borate esterification method, and when n(phenol):n(formaldehyde) is 1:1.5, the corresponding BPF exhibits the best heat resistance. The thermal analysis results show that the char yield of BPF is 78% at 1000℃, which is better than those of traditional phenolic resin and commercially available boron phenolic resin. The influence of boric acid content on the heat resistance of BPF was also discussed. When n(boric acid):n(phenol) is more than 0.33:1, the char yield of BPF tends to be constant. In addition, the pre-curing and the post curing temperatures of BPF determined by DSC analysis are 160℃ and 220℃, respectively.
Phenolic resin(PF) is widely used due to its excellent heat resistance and mechanical properties. But its heat resistance cannot meet the demand of modern science and technology. Preparation of boron phenolic resin(BPF) with excellent high temperature resistance through borate esterification method, and when n(phenol):n(formaldehyde) is 1:1.5, the corresponding BPF exhibits the best heat resistance. The thermal analysis results show that the char yield of BPF is 78% at 1000℃, which is better than those of traditional phenolic resin and commercially available boron phenolic resin. The influence of boric acid content on the heat resistance of BPF was also discussed. When n(boric acid):n(phenol) is more than 0.33:1, the char yield of BPF tends to be constant. In addition, the pre-curing and the post curing temperatures of BPF determined by DSC analysis are 160℃ and 220℃, respectively.
2017, 34(6): 636-643
doi: 10.11944/j.issn.1000-0518.2017.06.160358
Abstract:
A novel method for preparation of high-solubility polyaniline(PANI) by one-step emulsion polymerization was reported with poly(2-acrylamide-2-methyl-1 propane sulfonic acid)(PAMPS) as doping acid and emulsifier by utilizing its unique long chain, hydrophilicity, and strong acid group. The structure and properties of the final product were investigated by nuclear magnetic resonance spectroscopy(NMR), Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). The results shows that in the optimal preparation conditions of the reaction time 5 h, the polymerization temperature 5 ℃, the m(AN):m(AMPS):m(APS)=1:2:1.5, the mass fraction of AMPS and APS 20% and 30%, respectively, the yield of PANI is 86%, the electrical conductivity reaches 5.9 S/cm and the solubilities in organic solvent of DMF and water are 38% and over 21%, respectively.
A novel method for preparation of high-solubility polyaniline(PANI) by one-step emulsion polymerization was reported with poly(2-acrylamide-2-methyl-1 propane sulfonic acid)(PAMPS) as doping acid and emulsifier by utilizing its unique long chain, hydrophilicity, and strong acid group. The structure and properties of the final product were investigated by nuclear magnetic resonance spectroscopy(NMR), Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). The results shows that in the optimal preparation conditions of the reaction time 5 h, the polymerization temperature 5 ℃, the m(AN):m(AMPS):m(APS)=1:2:1.5, the mass fraction of AMPS and APS 20% and 30%, respectively, the yield of PANI is 86%, the electrical conductivity reaches 5.9 S/cm and the solubilities in organic solvent of DMF and water are 38% and over 21%, respectively.
2017, 34(6): 644-648
doi: 10.11944/j.issn.1000-0518.2017.06.160372
Abstract:
Separation membrane is widely used in various separation processes such as in wastewater treatment, medicine, food and dairy processing, and chemical engineering.However, membranes are easily to be fouled by proteins and microbes, which decrease the membrane performance and lifetime. As a result, separation membranes can be expensive which inhibit it's wide use. In this study, cardo poly(aryl ether ketone) containing carboxyl(PEK-COOH) was used to fabricate ultrafiltration membrane. Lysine(Lys), arginine(Arg) and histidine(His) were introduced to the PEK-COOH membrane surface via 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide(EDC)/N-hydroxysuccinimide(NHS) method. The results show that the pure water flux increases compared with PEK-COOH membrane. Also, the amino acid modified membranes are resistant to protein adsorption. Furthermore, the flux recovery ratio of His-modified membrane is 80% after three cycles during the bovine serum albumin(BSA) solution filtration process, indicating a high antifouling property.
Separation membrane is widely used in various separation processes such as in wastewater treatment, medicine, food and dairy processing, and chemical engineering.However, membranes are easily to be fouled by proteins and microbes, which decrease the membrane performance and lifetime. As a result, separation membranes can be expensive which inhibit it's wide use. In this study, cardo poly(aryl ether ketone) containing carboxyl(PEK-COOH) was used to fabricate ultrafiltration membrane. Lysine(Lys), arginine(Arg) and histidine(His) were introduced to the PEK-COOH membrane surface via 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide(EDC)/N-hydroxysuccinimide(NHS) method. The results show that the pure water flux increases compared with PEK-COOH membrane. Also, the amino acid modified membranes are resistant to protein adsorption. Furthermore, the flux recovery ratio of His-modified membrane is 80% after three cycles during the bovine serum albumin(BSA) solution filtration process, indicating a high antifouling property.
2017, 34(6): 649-655
doi: 10.11944/j.issn.1000-0518.2017.06.160394
Abstract:
In order to solve poor color fastness and serious color transfer of the traditional color polyurethane leather because of weak interaction(intermolecular force) between polyurethane and color base. A kind of reactive color diol was synthesized as follows:p-aminoacetanilide with a yield of 85% was prepared by acylation of p-phenylenediamine with acetic anhydride in tetrahydrofuran at 0~5℃ for 15 h, during which the molar ratio of p-phenylenediamine to acetic anhydride was 1.00:0.95. Then its diazonium salt was coupled with an excess molar fraction of 5% N-phenyl-diethanolamine to obtain 4-acetylamino-4'-N, N-dihydroxyethylamino azobenzene with yield of 82%. The reactive color diol was mixed with polyester or polyether diol in different proportions, followed by prepolymering, chain extension with diisocyanate to form polyurethane resin color paste whose crack-growth rate, relative breaking strength, and color transfer are 443%, 125.5 g and 21.4 μg, respectively, when spreaded into a film. And those of the similar film obtained from import diol are 442.2%, 125.3 g and 29.2 μg, respectively, indicating that the synthetic color diol is superior to the imported product.
In order to solve poor color fastness and serious color transfer of the traditional color polyurethane leather because of weak interaction(intermolecular force) between polyurethane and color base. A kind of reactive color diol was synthesized as follows:p-aminoacetanilide with a yield of 85% was prepared by acylation of p-phenylenediamine with acetic anhydride in tetrahydrofuran at 0~5℃ for 15 h, during which the molar ratio of p-phenylenediamine to acetic anhydride was 1.00:0.95. Then its diazonium salt was coupled with an excess molar fraction of 5% N-phenyl-diethanolamine to obtain 4-acetylamino-4'-N, N-dihydroxyethylamino azobenzene with yield of 82%. The reactive color diol was mixed with polyester or polyether diol in different proportions, followed by prepolymering, chain extension with diisocyanate to form polyurethane resin color paste whose crack-growth rate, relative breaking strength, and color transfer are 443%, 125.5 g and 21.4 μg, respectively, when spreaded into a film. And those of the similar film obtained from import diol are 442.2%, 125.3 g and 29.2 μg, respectively, indicating that the synthetic color diol is superior to the imported product.
2017, 34(6): 656-663
doi: 10.11944/j.issn.1000-0518.2017.06.160382
Abstract:
Visible-light responsive photocatalyst Bi20TiO32 was prepared through solvothermal method. To achieve the immobilization of photocatalysts, Bi20TiO32/polyacrylonitrile(PAN) composite nanofibers with different content of Bi20TiO32 were prepared by coaxial electrospinning method. Through this approach, the photocatalysts could be easily recycled, meanwhile, the contact area between photocatalysts and organic pollutants was enhanced during the degradation reaction. The prepared samples were characterized by X-ray diffraction spectra(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), ultraviolet-visible(UV-Vis) diffuse reflectance spectra(UV-Vis DRS) and N2 adsorption-desorption analysis. The photocatalytic activities of Bi20TiO32/PAN composite nanofibers were evaluated by the degradation of isoproturon herbicide under visible-light irradiation. The results show that the prepared Bi20TiO32 photocatalyst with a band gap energy 2.35 eV has a typical visible-light responsive property. The diameters of Bi20TiO32/PAN composite nanofibers are 600~700 nm. Bi20TiO32 is successfully loaded on the surface of nanofibers by this method and the composite materials have obvious visible-light responsibilities. The prepared samples exhibit great photocatalytic activity for degradation of isoproturon. The sample S3 at photocatalyst content 25.7% exhibits the highest removal efficiency of 87%. This research indicates that the photocatalysts immobilized on the organic nanofibers surface can retain their original photocatalytic activity. Coaxial electrospinning technology is a proper approach for the immobilization of photocatalysts.
Visible-light responsive photocatalyst Bi20TiO32 was prepared through solvothermal method. To achieve the immobilization of photocatalysts, Bi20TiO32/polyacrylonitrile(PAN) composite nanofibers with different content of Bi20TiO32 were prepared by coaxial electrospinning method. Through this approach, the photocatalysts could be easily recycled, meanwhile, the contact area between photocatalysts and organic pollutants was enhanced during the degradation reaction. The prepared samples were characterized by X-ray diffraction spectra(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), ultraviolet-visible(UV-Vis) diffuse reflectance spectra(UV-Vis DRS) and N2 adsorption-desorption analysis. The photocatalytic activities of Bi20TiO32/PAN composite nanofibers were evaluated by the degradation of isoproturon herbicide under visible-light irradiation. The results show that the prepared Bi20TiO32 photocatalyst with a band gap energy 2.35 eV has a typical visible-light responsive property. The diameters of Bi20TiO32/PAN composite nanofibers are 600~700 nm. Bi20TiO32 is successfully loaded on the surface of nanofibers by this method and the composite materials have obvious visible-light responsibilities. The prepared samples exhibit great photocatalytic activity for degradation of isoproturon. The sample S3 at photocatalyst content 25.7% exhibits the highest removal efficiency of 87%. This research indicates that the photocatalysts immobilized on the organic nanofibers surface can retain their original photocatalytic activity. Coaxial electrospinning technology is a proper approach for the immobilization of photocatalysts.
2017, 34(6): 664-670
doi: 10.11944/j.issn.1000-0518.2017.06.160379
Abstract:
In order to synthesize selaginellin family natural products, a methodology of 1, 6-addition of alkynyl lithium to p-quinone methides was developed. The reaction conditions and scope and limitations of substrates of this reaction were investigated. The results show that the electronic effect of substituents on the phenyl ring of p-quinone methides exhibits significant effects on reaction rates and yields. Electro-withdrawing groups accelerate the addition and lead to good yields. On the other hand, electro-donating groups deactivate p-quinone methides, and low yield is observed presumably due to the equilibrium nature of the reaction. Besides, all alkynes surveyed provide corresponding products in high yield. This novel method can provide a rapid assembly of the skeleton of selaginellin natural products.
In order to synthesize selaginellin family natural products, a methodology of 1, 6-addition of alkynyl lithium to p-quinone methides was developed. The reaction conditions and scope and limitations of substrates of this reaction were investigated. The results show that the electronic effect of substituents on the phenyl ring of p-quinone methides exhibits significant effects on reaction rates and yields. Electro-withdrawing groups accelerate the addition and lead to good yields. On the other hand, electro-donating groups deactivate p-quinone methides, and low yield is observed presumably due to the equilibrium nature of the reaction. Besides, all alkynes surveyed provide corresponding products in high yield. This novel method can provide a rapid assembly of the skeleton of selaginellin natural products.
2017, 34(6): 671-675
doi: 10.11944/j.issn.1000-0518.2017.06.160354
Abstract:
The method of synthesis of 4-methyl-4-aza-21E-benzylidene-5-pregnene-3, 20-dione catalyzed by KF/Al2O3 was reported. 4-Methyl-4-aza-5-pregnene-3, 20-dione, as a key intermediate, was synthesized by cleavage of A-ring and ring-closure from progesterone and which was then converted to the target product through Claisen condensation catalyzed by KF/Al2O3. The effects of different catalysts, reaction temperature and catalyst dosage were investigated. 56%~68% yields are obtained under optimal conditions:n(3):n(KF/Al2O3)=1:1, reaction time 4 h under reflux. This study provides a simple and efficient approach to the synthesis of 4-aza-steroidal benzylidene derivatives.
The method of synthesis of 4-methyl-4-aza-21E-benzylidene-5-pregnene-3, 20-dione catalyzed by KF/Al2O3 was reported. 4-Methyl-4-aza-5-pregnene-3, 20-dione, as a key intermediate, was synthesized by cleavage of A-ring and ring-closure from progesterone and which was then converted to the target product through Claisen condensation catalyzed by KF/Al2O3. The effects of different catalysts, reaction temperature and catalyst dosage were investigated. 56%~68% yields are obtained under optimal conditions:n(3):n(KF/Al2O3)=1:1, reaction time 4 h under reflux. This study provides a simple and efficient approach to the synthesis of 4-aza-steroidal benzylidene derivatives.
2017, 34(6): 676-684
doi: 10.11944/j.issn.1000-0518.2017.06.160397
Abstract:
Sixteen liquid crystals with 3, 3, 3-trifluoropropynyl terminal group were reported. The target compounds were synthesized via a series of reactions including the zinc reagent's reaction, Suzuki cross-coupling, and the elimination reaction of HCl. The total yields are more than 67%, and the gas chromatograph(GC) purities are more than 99.5%. The structures of the target compounds were characterized by infrared spectroscopy(IR), nuclear magnetic resonance(NMR) and mass spectrometry(MS). Moreover, their thermal properties were investigated by differential scanning calorimetry(DSC) and polarizing microscope(POM). The results show that the biphenyl type of compounds exists no liquid crystal phase while the terphenyl compounds have a smectic A phase. The melting points drop with the increase in the number of alkyl chain carbon. In terms of physical properties, these compounds have large Δε value(12.61~21.94), and the value of Δε is increased by trifluoromethyl and lateral fluorine substitution. The Δn value is about 0.19~0.29 with the increase of the number of benzene rings. The γ1 value is in the range from 49.9 to 468.0 mPa·s, which goes up with the increase of the number of benzene rings. Compounds 4n have high Δε(>19.2), high ε⊥(>10.3), and low Δε/ε⊥( < 2). The influence of the position of the acetylenic bond on the properties of this kind of liquid crystal was discussed by simulation. All of the above properties of these liquid crystals have been proved to be useful for tuning the birefringence and the dielectric anisotropy of the liquid crystal mixtures, and these liquid crystals also have good value for FFS(fringe-field switching) display mode by the improvement of molecular structure.
Sixteen liquid crystals with 3, 3, 3-trifluoropropynyl terminal group were reported. The target compounds were synthesized via a series of reactions including the zinc reagent's reaction, Suzuki cross-coupling, and the elimination reaction of HCl. The total yields are more than 67%, and the gas chromatograph(GC) purities are more than 99.5%. The structures of the target compounds were characterized by infrared spectroscopy(IR), nuclear magnetic resonance(NMR) and mass spectrometry(MS). Moreover, their thermal properties were investigated by differential scanning calorimetry(DSC) and polarizing microscope(POM). The results show that the biphenyl type of compounds exists no liquid crystal phase while the terphenyl compounds have a smectic A phase. The melting points drop with the increase in the number of alkyl chain carbon. In terms of physical properties, these compounds have large Δε value(12.61~21.94), and the value of Δε is increased by trifluoromethyl and lateral fluorine substitution. The Δn value is about 0.19~0.29 with the increase of the number of benzene rings. The γ1 value is in the range from 49.9 to 468.0 mPa·s, which goes up with the increase of the number of benzene rings. Compounds 4n have high Δε(>19.2), high ε⊥(>10.3), and low Δε/ε⊥( < 2). The influence of the position of the acetylenic bond on the properties of this kind of liquid crystal was discussed by simulation. All of the above properties of these liquid crystals have been proved to be useful for tuning the birefringence and the dielectric anisotropy of the liquid crystal mixtures, and these liquid crystals also have good value for FFS(fringe-field switching) display mode by the improvement of molecular structure.
2017, 34(6): 693-699
doi: 10.11944/j.issn.1000-0518.2017.06.160307
Abstract:
A three-dimensional(3D)zinc compound [Zn(3-bpye)(H2Mo4O14)(H2O)2](3-bpye=N, N'-bis(3-pyridinecarboxamide)-1, 2-ethane) based on one-dimensional(1D) [H2Mo4O14]n2n- chain was hydrothermally prepared by bis(pyridyl)-bis(amide) ligand, ammonium molybdate and zinc chloride. Structural analysis by element analysis, indrared(IR) spectroscopy, thermogravity(TG) and X-ray single-crystal diffraction(XRD) reveal that the title compound is triclinic system with P-1 space group. Its cell parameters are a=0.61310(3) nm, b=1.04750(6) nm, c=1.06540(6) nm, α=78.5540(10)°, β=77.5350(10)°, γ=89.9050(10)°, V=0.65420(6) nm3, Mr=981.47, Dc=2.491 g/cm3, Z=1, F(000)=468, R1=0.0290, ωR2=0.1068. In the title compound, 1D [H2Mo4O14]n2n- chains are linked by the Zn2+ ions to form 2D inorganic bimetallic layer [Zn(H2Mo4O14)]n. The adjacent 2D layers are further connected by the bridging ligands 3-bpye to construct 3D framework with CdSO4 topology. This zinc compound possesses strong fluorescence emission. Moreover, this compound shows remarkable photocatalytic activities for the degradation of methylene blue and rhodamine B under ultraviolet irradiation. CCDC: 1493115.
A three-dimensional(3D)zinc compound [Zn(3-bpye)(H2Mo4O14)(H2O)2](3-bpye=N, N'-bis(3-pyridinecarboxamide)-1, 2-ethane) based on one-dimensional(1D) [H2Mo4O14]n2n- chain was hydrothermally prepared by bis(pyridyl)-bis(amide) ligand, ammonium molybdate and zinc chloride. Structural analysis by element analysis, indrared(IR) spectroscopy, thermogravity(TG) and X-ray single-crystal diffraction(XRD) reveal that the title compound is triclinic system with P-1 space group. Its cell parameters are a=0.61310(3) nm, b=1.04750(6) nm, c=1.06540(6) nm, α=78.5540(10)°, β=77.5350(10)°, γ=89.9050(10)°, V=0.65420(6) nm3, Mr=981.47, Dc=2.491 g/cm3, Z=1, F(000)=468, R1=0.0290, ωR2=0.1068. In the title compound, 1D [H2Mo4O14]n2n- chains are linked by the Zn2+ ions to form 2D inorganic bimetallic layer [Zn(H2Mo4O14)]n. The adjacent 2D layers are further connected by the bridging ligands 3-bpye to construct 3D framework with CdSO4 topology. This zinc compound possesses strong fluorescence emission. Moreover, this compound shows remarkable photocatalytic activities for the degradation of methylene blue and rhodamine B under ultraviolet irradiation. CCDC: 1493115.
2017, 34(6): 700-704
doi: 10.11944/j.issn.1000-0518.2017.06.160370
Abstract:
In this study, we synthesised five kinds of Keggin-type transition metal substituted polyoxometalates(Na7PMo11M(Ⅱ)O40(M=Mn, Fe, Zn, Co, Ni), abbreviated as PMo11M(Ⅱ)(M=Mn, Fe, Zn, Co, Ni)). The structures of these compounds were characterized by UV-visible absorption spectrum and Fourier transform infrared spectrometer(FTIR). And then the antibacterial activities of the five kinds of Keggin-type transition metal substituted polyoxometalates(PMo11M(Ⅱ)(M=Mn, Fe, Zn, Co, Ni) and their parent H3PMo12O40(abbreviated PMo12) on Sarcina lutea(S.lutea), Staphylococcus aureus(S.aureus), Bacillus subtilis(B.subtilis) and Escherichia coli(E.coli) were investigated by Oxford plate. Also, the minimum inhibitory concentration(MIC) and the minimum bactericidal concentration(MBC) were tested by broth microdilution methods. The results show that the six kinds of polyoxometalates can inhibit the proliferation of these four different kinds of bacteria to different extents, and the antimicrobial activities of all compounds on S.lutea and S.aureus are more effective than those against B.Subtilis and E.coli. Among these compounds, the antibacterial activities of (PMo11M(Ⅱ)(M=Ni, Mn, Zn)) were superior to the other three compounds. This study will provide more theoretical and experimental supports for polyoxometalates as preservative agents in fruit and vegetables.
In this study, we synthesised five kinds of Keggin-type transition metal substituted polyoxometalates(Na7PMo11M(Ⅱ)O40(M=Mn, Fe, Zn, Co, Ni), abbreviated as PMo11M(Ⅱ)(M=Mn, Fe, Zn, Co, Ni)). The structures of these compounds were characterized by UV-visible absorption spectrum and Fourier transform infrared spectrometer(FTIR). And then the antibacterial activities of the five kinds of Keggin-type transition metal substituted polyoxometalates(PMo11M(Ⅱ)(M=Mn, Fe, Zn, Co, Ni) and their parent H3PMo12O40(abbreviated PMo12) on Sarcina lutea(S.lutea), Staphylococcus aureus(S.aureus), Bacillus subtilis(B.subtilis) and Escherichia coli(E.coli) were investigated by Oxford plate. Also, the minimum inhibitory concentration(MIC) and the minimum bactericidal concentration(MBC) were tested by broth microdilution methods. The results show that the six kinds of polyoxometalates can inhibit the proliferation of these four different kinds of bacteria to different extents, and the antimicrobial activities of all compounds on S.lutea and S.aureus are more effective than those against B.Subtilis and E.coli. Among these compounds, the antibacterial activities of (PMo11M(Ⅱ)(M=Ni, Mn, Zn)) were superior to the other three compounds. This study will provide more theoretical and experimental supports for polyoxometalates as preservative agents in fruit and vegetables.
2017, 34(6): 705-711
doi: 10.11944/j.issn.1000-0518.2017.06.160329
Abstract:
Using non-through-hole anodic aluminum oxide(AAO) as templates, with Al substrate as support body, Pd nanomaterials were prepared in situ in the channels of AAO with Al substrate as reducing agent. The removal of barrier layer and acid corrosion post-treatment of synthesized Pd/AAO were studied. The Pd morphologies under different situations were observed by scanning electronic microscopy. A plausible mechanism of Pd formation was proposed. The catalytic activity for Suzuki reaction of 4-bromobenzene carboxylic acid and phenylboronic acid was investigated with Pd/AAO as heterogeneous catalysts. It is found that Pd/AAO catalysts exhibit excellent catalytic activity, and the yield is up to 99.8% with 0.06% molar fraction of Pd. The catalysts with sheet structure are easily separated for recovery by just taking out of the solution and can be reused in the next time. This research gives a practical method for the design of heterogeneous catalysts in organic reactions.
Using non-through-hole anodic aluminum oxide(AAO) as templates, with Al substrate as support body, Pd nanomaterials were prepared in situ in the channels of AAO with Al substrate as reducing agent. The removal of barrier layer and acid corrosion post-treatment of synthesized Pd/AAO were studied. The Pd morphologies under different situations were observed by scanning electronic microscopy. A plausible mechanism of Pd formation was proposed. The catalytic activity for Suzuki reaction of 4-bromobenzene carboxylic acid and phenylboronic acid was investigated with Pd/AAO as heterogeneous catalysts. It is found that Pd/AAO catalysts exhibit excellent catalytic activity, and the yield is up to 99.8% with 0.06% molar fraction of Pd. The catalysts with sheet structure are easily separated for recovery by just taking out of the solution and can be reused in the next time. This research gives a practical method for the design of heterogeneous catalysts in organic reactions.
2017, 34(6): 712-722
doi: 10.11944/j.issn.1000-0518.2017.06.160357
Abstract:
Lithium vanadium phosphate(Li3V2(PO4)3)/reduced graphene oxide(rGO) composite has been successfully synthesized by incorporating melamine resin(MR) functionalized GO precursor into the Li3V2(PO4)3 solution and the subsequent heat treatment. The structural and electrochemical properties of Li3V2(PO4)3/rGO were characterized. The results show that Li3V2(PO4)3/rGO composite has monoclinic system, restacking of graphene layers and agglomeration of Li3V2(PO4)3 particles have been greatly inhibited, electrochemical performance of the composite has been improved. The as-obtained Li3V2(PO4)3/rGO was used as the cathode material in lithium ion batteries. The very low degree of polarization in the curve shows that electron and ion transports are facile, thus good rate and cycle behavior are observed. A considerably high lithiation capacity of 86 mA·h/g can be retained even at 20 C in the range of 3.0~4.3 V. After 100 cycles at 0.1 C, a discharge capacity of 119.7 mA·h/g could be delivered with the capacity retention of 94%. When the cells are operated between the voltage limits of 3.0~4.8 V vs.Li+/Li, a lithiation capacity of 80 mA·h/g at 10 C and 145.6 mA·h/g at 0.1 C after 100 cycles could be retained. Good cycling and rate performances, together with low carbon content, will be satisfactory for use as cathode material in lithium ion batteries.
Lithium vanadium phosphate(Li3V2(PO4)3)/reduced graphene oxide(rGO) composite has been successfully synthesized by incorporating melamine resin(MR) functionalized GO precursor into the Li3V2(PO4)3 solution and the subsequent heat treatment. The structural and electrochemical properties of Li3V2(PO4)3/rGO were characterized. The results show that Li3V2(PO4)3/rGO composite has monoclinic system, restacking of graphene layers and agglomeration of Li3V2(PO4)3 particles have been greatly inhibited, electrochemical performance of the composite has been improved. The as-obtained Li3V2(PO4)3/rGO was used as the cathode material in lithium ion batteries. The very low degree of polarization in the curve shows that electron and ion transports are facile, thus good rate and cycle behavior are observed. A considerably high lithiation capacity of 86 mA·h/g can be retained even at 20 C in the range of 3.0~4.3 V. After 100 cycles at 0.1 C, a discharge capacity of 119.7 mA·h/g could be delivered with the capacity retention of 94%. When the cells are operated between the voltage limits of 3.0~4.8 V vs.Li+/Li, a lithiation capacity of 80 mA·h/g at 10 C and 145.6 mA·h/g at 0.1 C after 100 cycles could be retained. Good cycling and rate performances, together with low carbon content, will be satisfactory for use as cathode material in lithium ion batteries.
2017, 34(6): 723-728
doi: 10.11944/j.issn.1000-0518.2017.06.160376
Abstract:
High performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry(HPLC-Q-TOF MS/MS) were used for the comparative analysis of the content of ginsenosides in the decoction of Panax ginseng with hawthorn and hydrolysis of ginsenosides in compatibility of ginsenosides Re, Rg1, Rb1, Rd with hawthorn, single decoction and simulated pH value decoction. The results show that the contents of ginsenosides Rg1 and Rb1 decrease, while the contents of ginsenosides Re, Rd, Rg2, Rg3, F2, Rh1 increase in ginseng-hawthorn combined decoction. Ginsenosides 20(R)-Rg2, 20(S)-Rg2 are the hydrolysates when ginsenoside Re and hawthorn are boiled together, while others are ginsenosides 20(R)-Rg2, 20(S)-Rg2, Rg4 and Rg6 when ginsenoside Re is boiled in the same pH value without hawthorn. In addition, the hydrolysates are ginsenosides 20(S)-Rh1 and 20(R)-Rh1 in ginsenoside Rg1-hawthorn combined decoction, but ginsenosides 20(S)-Rh1, 20(R)-Rh1, Rh4, Rk3 are determined in the simulated pH value decoction. Ginsenosides Rd, 20(S)-Rg3 are the major hydrolysates in co-decoction of ginsenoside Rb1 and hawthorn, while ginsenosides F2, 20(S)-Rg3 are the major hydrolysates from the simulated pH value decoction. Ginsenosides F2, 20(R)-Rg3, 20(S)-Rg3 are hydrolysates in ginsenoside Rd-hawthorn combined decoction, but ginsenosides 20(R)-Rg3, 20(S)-Rg3 are hydrolysates in the simulated pH value decoction. The hydrolysis of ginsenosides is different in the processes of co-decoction with hawthorn and the simulated pH value decoction, which may be the basis of chemical composition in combination of Panax ginseng and hawthorn. It provides the material bases for combination of Panax ginseng and hawthorn in prescriptions of traditional Chinese medicine.
High performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry(HPLC-Q-TOF MS/MS) were used for the comparative analysis of the content of ginsenosides in the decoction of Panax ginseng with hawthorn and hydrolysis of ginsenosides in compatibility of ginsenosides Re, Rg1, Rb1, Rd with hawthorn, single decoction and simulated pH value decoction. The results show that the contents of ginsenosides Rg1 and Rb1 decrease, while the contents of ginsenosides Re, Rd, Rg2, Rg3, F2, Rh1 increase in ginseng-hawthorn combined decoction. Ginsenosides 20(R)-Rg2, 20(S)-Rg2 are the hydrolysates when ginsenoside Re and hawthorn are boiled together, while others are ginsenosides 20(R)-Rg2, 20(S)-Rg2, Rg4 and Rg6 when ginsenoside Re is boiled in the same pH value without hawthorn. In addition, the hydrolysates are ginsenosides 20(S)-Rh1 and 20(R)-Rh1 in ginsenoside Rg1-hawthorn combined decoction, but ginsenosides 20(S)-Rh1, 20(R)-Rh1, Rh4, Rk3 are determined in the simulated pH value decoction. Ginsenosides Rd, 20(S)-Rg3 are the major hydrolysates in co-decoction of ginsenoside Rb1 and hawthorn, while ginsenosides F2, 20(S)-Rg3 are the major hydrolysates from the simulated pH value decoction. Ginsenosides F2, 20(R)-Rg3, 20(S)-Rg3 are hydrolysates in ginsenoside Rd-hawthorn combined decoction, but ginsenosides 20(R)-Rg3, 20(S)-Rg3 are hydrolysates in the simulated pH value decoction. The hydrolysis of ginsenosides is different in the processes of co-decoction with hawthorn and the simulated pH value decoction, which may be the basis of chemical composition in combination of Panax ginseng and hawthorn. It provides the material bases for combination of Panax ginseng and hawthorn in prescriptions of traditional Chinese medicine.
2017, 34(6): 729-732
doi: 10.11944/j.issn.1000-0518.2017.06.160392
Abstract:
In this research, argon was used as the running gas in direct analysis in real time mass spectrometry instead of helium in order to reduce the cost of experiment. Methanol and alcohol as reactive reagents improve the ionization efficiency of analytes and expand the application of Ar-DART-MS. This is because the above reagents play important roles as the medium of the energy transferring and the domor of proton in Ar-DART-MS analysis. Through the analysis of background signal from methol and alcohol as reactive reagents in Ar-DART-MS and their affect on sample ionization, the application scope of methanol and alcohol as reactive reagents in Ar-DART-MS was discussed. Some possible characteristic reactions were also explored. The validity of this method was verified by the analysis of reserpine.
In this research, argon was used as the running gas in direct analysis in real time mass spectrometry instead of helium in order to reduce the cost of experiment. Methanol and alcohol as reactive reagents improve the ionization efficiency of analytes and expand the application of Ar-DART-MS. This is because the above reagents play important roles as the medium of the energy transferring and the domor of proton in Ar-DART-MS analysis. Through the analysis of background signal from methol and alcohol as reactive reagents in Ar-DART-MS and their affect on sample ionization, the application scope of methanol and alcohol as reactive reagents in Ar-DART-MS was discussed. Some possible characteristic reactions were also explored. The validity of this method was verified by the analysis of reserpine.
2017, 34(6): 685-692
doi: 10.11944/j.issn.1000-0518.2017.06.160393
Abstract:
Perimidine is a multi-nuclear N-heterocyclic compound, which plays an important role in industrial and biological fields. Perimidines have been drawn extensive examinations from many researchers for a long time due to the nitrogen heterocyclic ring. Here, a series of perimidine derivatives(4a~4g and 6) was synthesized through 1, 8-diaminonaphthalene and aldehydes. The products were characterized by infrared spectroscopy(IR), proton or carbon nuclear magnetic resonance(1H NMR, 13C NMR), high resolution mass spectrometry(HRMS). Compounds 4a and 6 were investigated by single-crystal X-ray diffraction. X-ray analysis reveals that both of crystals of 4a and 6 are made up of monoclinic unit cells with space group P21/n. In addition, the biological activity assay was carried out. The results show that perimidine derivatives have a diverse range of biological activities against the fungi, which indicates that perimidine derivatives have great potential applications in antibacterial fields in the future. And test data indicate that there is no obvious regulation between fungicidal activity and the different substituents on the benzene ring.
Perimidine is a multi-nuclear N-heterocyclic compound, which plays an important role in industrial and biological fields. Perimidines have been drawn extensive examinations from many researchers for a long time due to the nitrogen heterocyclic ring. Here, a series of perimidine derivatives(4a~4g and 6) was synthesized through 1, 8-diaminonaphthalene and aldehydes. The products were characterized by infrared spectroscopy(IR), proton or carbon nuclear magnetic resonance(1H NMR, 13C NMR), high resolution mass spectrometry(HRMS). Compounds 4a and 6 were investigated by single-crystal X-ray diffraction. X-ray analysis reveals that both of crystals of 4a and 6 are made up of monoclinic unit cells with space group P21/n. In addition, the biological activity assay was carried out. The results show that perimidine derivatives have a diverse range of biological activities against the fungi, which indicates that perimidine derivatives have great potential applications in antibacterial fields in the future. And test data indicate that there is no obvious regulation between fungicidal activity and the different substituents on the benzene ring.
