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2016 Volume 33 Issue 1
2016, 33(1): 1-17
doi: 10.11944/j.issn.1000-0518.2016.01.150399
Abstract:
The device efficiency and thermal stability are two crucial factors in realizing the commercial application of polymer solar cells(PSCs). The power conversion efficiency(PCE) has been boosted up over 10% during the last decade. And a lot of work was directed at improving the thermal stability of device. In this paper, the development of morphological stability on polymer solar cells is reviewed. Several approaches of improving the morphological stability are illustrated in detail. And a promising future perspective is presented.
The device efficiency and thermal stability are two crucial factors in realizing the commercial application of polymer solar cells(PSCs). The power conversion efficiency(PCE) has been boosted up over 10% during the last decade. And a lot of work was directed at improving the thermal stability of device. In this paper, the development of morphological stability on polymer solar cells is reviewed. Several approaches of improving the morphological stability are illustrated in detail. And a promising future perspective is presented.
2016, 33(1): 18-24
doi: 10.11944/j.issn.1000-0518.2016.01.150308
Abstract:
Although they show high power density, supercapacitors often suffer from low energy density. As a new kind of supercapacitors, colloidal ion supercapacitors that include various transition metal cations and rare earth cations, such as Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Sn2+, Sn4+, La3+, Ce3+, Er3+, Yb3+, etc, show both high energy density and high power density. Proper evaluation of specific capacitance of colloidal ion supercapacitors can deepen our understanding of the electrochemical mechanism of electroactive cations in pseudocapacitive electrode materials. This review firstly outlines the basic concept of colloidal ion supercapacitors and in situ coprecipitation synthesis methods. Then the specific capacitance based on active cations(named cationic capacitance) is used to evaluate the performance of colloidal ion supercapacitors. We then calculate the specific capacitances on the basis of hydroxides and oxides(named hydroxide capacitance and oxide capacitance), which are traditional evaluation methods for supercapacitors. Compared with three kinds of specific capacitances, cationic capacitance can really reflect the intrinsic reaction mechanism of pseudocapacitive materials. It is expected that colloidal ion supercapacitors can overcome the technical bottleneck of the existing electrochemical energy storage devices and be the next-generation high-energy storage devices.
Although they show high power density, supercapacitors often suffer from low energy density. As a new kind of supercapacitors, colloidal ion supercapacitors that include various transition metal cations and rare earth cations, such as Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Sn2+, Sn4+, La3+, Ce3+, Er3+, Yb3+, etc, show both high energy density and high power density. Proper evaluation of specific capacitance of colloidal ion supercapacitors can deepen our understanding of the electrochemical mechanism of electroactive cations in pseudocapacitive electrode materials. This review firstly outlines the basic concept of colloidal ion supercapacitors and in situ coprecipitation synthesis methods. Then the specific capacitance based on active cations(named cationic capacitance) is used to evaluate the performance of colloidal ion supercapacitors. We then calculate the specific capacitances on the basis of hydroxides and oxides(named hydroxide capacitance and oxide capacitance), which are traditional evaluation methods for supercapacitors. Compared with three kinds of specific capacitances, cationic capacitance can really reflect the intrinsic reaction mechanism of pseudocapacitive materials. It is expected that colloidal ion supercapacitors can overcome the technical bottleneck of the existing electrochemical energy storage devices and be the next-generation high-energy storage devices.
2016, 33(1): 25-31
doi: 10.11944/j.issn.1000-0518.2016.01.150182
Abstract:
To discover efficient structural modification strategy for the conversion of antibacterial activity of fluoroquinolones into antitumor activity, an azole heterocycle modified with sulfide-ketone thiosemicarbazone chain was designed as the bioisosteric replacement of the C-3 carboxylic acid group. Consequently, novel s-triazole-based thiosemicarbazone derivatives(6a~6g) were synthesized from ofloxacin 1, respectively. The structures of the title compounds(6a~6g) were characterized by elemental analysis and spectral data, and the in vitro antitumor activity was also evaluated by the MTT assay. Compounds(6a~6g) exhibit more significantly antiproliferative activity than both of parent ofloxacin 1 and the corresponding sulfide-ketone intermediates(5a~5g). These thiosemicarbazones, particularly those containing nitro group or fluorine atom, have comparable activity to doxorubicin. Therefore, it suggests that an azole ring modified with functional side-chain as the bioisosteric replacement of the C-3 carboxylic group is favorable for an improvement of antitumor activity of fluoroquinolones.
To discover efficient structural modification strategy for the conversion of antibacterial activity of fluoroquinolones into antitumor activity, an azole heterocycle modified with sulfide-ketone thiosemicarbazone chain was designed as the bioisosteric replacement of the C-3 carboxylic acid group. Consequently, novel s-triazole-based thiosemicarbazone derivatives(6a~6g) were synthesized from ofloxacin 1, respectively. The structures of the title compounds(6a~6g) were characterized by elemental analysis and spectral data, and the in vitro antitumor activity was also evaluated by the MTT assay. Compounds(6a~6g) exhibit more significantly antiproliferative activity than both of parent ofloxacin 1 and the corresponding sulfide-ketone intermediates(5a~5g). These thiosemicarbazones, particularly those containing nitro group or fluorine atom, have comparable activity to doxorubicin. Therefore, it suggests that an azole ring modified with functional side-chain as the bioisosteric replacement of the C-3 carboxylic group is favorable for an improvement of antitumor activity of fluoroquinolones.
2016, 33(1): 32-38
doi: 10.11944/j.issn.1000-0518.2016.01.150252
Abstract:
In this work, a novel asymmetric pentamethine cyanine(Cy5) dye containing one nonionic hydrophilic group with two polyethylene glycol(PEG) ether chains on the indoline "N" was synthesized and characterized by 1H nuclear magnetic resonance(1H NMR) and high resolution mass spectrometer(HRMS). The spectra character and light stability of this Cy5 were investigated. The results show that the λab and λem of the dye in water are 648 nm and 668 nm, respectively, and Stokes shifts reach 20 nm. The fluorescence quantum yield(Ф) in water is 0.13. After irradiated for 8 h, the photo-degradation of the aqueous soluble dyestuff of 5.8% happens. Albumin Bovine Serum(BSA) is labeled with this Cy5, and the dye/protein molar ratio(D/P) of fluorescent labeling reachs 1.16. By comparing fixed cells staining and viable cells staining, it is found that fixed cells can be overall stained by the new Cy5, the nucleoli of which are the most obvious and can be seen clearly, and that a small amount of the new Cy5 across the cell membrane of viable cells into the cell can stain cytoplasm and cell nucleus weakly, but a lot of the dye clumps together in the viable cell membrane.
In this work, a novel asymmetric pentamethine cyanine(Cy5) dye containing one nonionic hydrophilic group with two polyethylene glycol(PEG) ether chains on the indoline "N" was synthesized and characterized by 1H nuclear magnetic resonance(1H NMR) and high resolution mass spectrometer(HRMS). The spectra character and light stability of this Cy5 were investigated. The results show that the λab and λem of the dye in water are 648 nm and 668 nm, respectively, and Stokes shifts reach 20 nm. The fluorescence quantum yield(Ф) in water is 0.13. After irradiated for 8 h, the photo-degradation of the aqueous soluble dyestuff of 5.8% happens. Albumin Bovine Serum(BSA) is labeled with this Cy5, and the dye/protein molar ratio(D/P) of fluorescent labeling reachs 1.16. By comparing fixed cells staining and viable cells staining, it is found that fixed cells can be overall stained by the new Cy5, the nucleoli of which are the most obvious and can be seen clearly, and that a small amount of the new Cy5 across the cell membrane of viable cells into the cell can stain cytoplasm and cell nucleus weakly, but a lot of the dye clumps together in the viable cell membrane.
2016, 33(1): 39-46
doi: 10.11944/j.issn.1000-0518.2016.01.150211
Abstract:
3-Nitroguanyl-6-(3,5-dimethylpyrazol-1yl)-1,2,4,5-tetrazine(NDT) was synthesized and its crystal structure was determined by X-ray diffraction analysis. Crystals of NDT·DMF have the following parameters:triclinic, space group P-1, a=0.7070(4) nm, b=0.8468(6) nm, c=1.4123(9) nm, α=73.281(8)°, β=80.423(11)°, γ=81.740(9)°, Z=2. Thermal decomposition behavior of NDT was studied by DSC and TG-DTG analysis. The apparent activation energy and pre-exponential constant of the exothermic decomposition reaction were obtained as 288.25 kJ/mol and 1029.04s-1, respectively. The self-accelerating decomposition temperature(TSADT), the thermal ignition temperature(Tbe) and the critical temperature of thermal explosion(Tbp) are 212.19℃, 213.52℃ and 214.95℃, respectively. The adiabatic time-to-explosion was also estimated to be 5.43~6.26 s.
3-Nitroguanyl-6-(3,5-dimethylpyrazol-1yl)-1,2,4,5-tetrazine(NDT) was synthesized and its crystal structure was determined by X-ray diffraction analysis. Crystals of NDT·DMF have the following parameters:triclinic, space group P-1, a=0.7070(4) nm, b=0.8468(6) nm, c=1.4123(9) nm, α=73.281(8)°, β=80.423(11)°, γ=81.740(9)°, Z=2. Thermal decomposition behavior of NDT was studied by DSC and TG-DTG analysis. The apparent activation energy and pre-exponential constant of the exothermic decomposition reaction were obtained as 288.25 kJ/mol and 1029.04s-1, respectively. The self-accelerating decomposition temperature(TSADT), the thermal ignition temperature(Tbe) and the critical temperature of thermal explosion(Tbp) are 212.19℃, 213.52℃ and 214.95℃, respectively. The adiabatic time-to-explosion was also estimated to be 5.43~6.26 s.
2016, 33(1): 47-52
doi: 10.11944/j.issn.1000-0518.2016.01.150174
Abstract:
A series of retardant polyurethanes(PUs) was synthesized from polylactide diol, hexamethylenediisocynate(HDI) and 2,2-bis(bromomethyl)-1,3-propanediol(DBNPG). The properties of PUs were characterized by FTIR, 1H NMR, mechanical test and GPC. The results show that DBNPG as a chain extender can meet the requirement of obtaining high molecular mass PUs. The longer chain of PLA and higher content of hard segment in PUs lead to an enhanced crystallinity of PUs. The tensile strength of PUs is close to 50 MPa, comparable to that of industrialized polylactide, showing a good mechanical property. The retardant ability of PUs increases with an increase of bromine mass fraction in PUs. Nonflammable PUs can be obtained when the mass fraction of bromine in PUs is beyond 8.6%.
A series of retardant polyurethanes(PUs) was synthesized from polylactide diol, hexamethylenediisocynate(HDI) and 2,2-bis(bromomethyl)-1,3-propanediol(DBNPG). The properties of PUs were characterized by FTIR, 1H NMR, mechanical test and GPC. The results show that DBNPG as a chain extender can meet the requirement of obtaining high molecular mass PUs. The longer chain of PLA and higher content of hard segment in PUs lead to an enhanced crystallinity of PUs. The tensile strength of PUs is close to 50 MPa, comparable to that of industrialized polylactide, showing a good mechanical property. The retardant ability of PUs increases with an increase of bromine mass fraction in PUs. Nonflammable PUs can be obtained when the mass fraction of bromine in PUs is beyond 8.6%.
2016, 33(1): 53-62
doi: 10.11944/j.issn.1000-0518.2016.01.150162
Abstract:
The esterification of chloromethylated polysulfone(CMPSF) with glyoxylic acid(GA) afforded aldehyde(AL) modified PSF-AL. Subsequent condensation of PSF-AL with 3-aminopyridine led to bidentate Schiff base ligand-functionalized PSF-AA. The chemical structure of PSF-AA was characterized by FTIR and 1H NMR spectra. The binary polymer-rare earth complexes of PSF-(AA)3-Tb(Ⅲ) and PSF-(AA)3-Eu(Ⅲ) were prepared and their photoluminescence properties were preliminarily explored. Optimized esterification between CMPSF and GA were performed in N,N-dimethylacetamide at 75℃. The macromolecular PSF-AA does not exhibit sensitization towards Eu(Ⅲ) ion, whereas PSF-AA can strongly sensitize the fluorescence emission of Tb(Ⅲ) ion. The complex PSF-(AA)3-Tb(Ⅲ) emits characteristic green fluorescence of Tb(Ⅲ) ion.
The esterification of chloromethylated polysulfone(CMPSF) with glyoxylic acid(GA) afforded aldehyde(AL) modified PSF-AL. Subsequent condensation of PSF-AL with 3-aminopyridine led to bidentate Schiff base ligand-functionalized PSF-AA. The chemical structure of PSF-AA was characterized by FTIR and 1H NMR spectra. The binary polymer-rare earth complexes of PSF-(AA)3-Tb(Ⅲ) and PSF-(AA)3-Eu(Ⅲ) were prepared and their photoluminescence properties were preliminarily explored. Optimized esterification between CMPSF and GA were performed in N,N-dimethylacetamide at 75℃. The macromolecular PSF-AA does not exhibit sensitization towards Eu(Ⅲ) ion, whereas PSF-AA can strongly sensitize the fluorescence emission of Tb(Ⅲ) ion. The complex PSF-(AA)3-Tb(Ⅲ) emits characteristic green fluorescence of Tb(Ⅲ) ion.
2016, 33(1): 63-69
doi: 10.11944/j.issn.1000-0518.2016.01.150169
Abstract:
In this article, a new Eu2+ ion activated silicate glass was prepared. The glass composition is 2CaO-MgO-3SiO2-0.015Eu2O3(CMSE). The transmitted spectrum, steady-state photoluminescence(PL) spectrum, long-lasting phosphorescence(LLP) and thermal glow were performed to investigate the luminescent properties of the CMSE sample. It was found that the CMSE sample can be excited by ultraviolet(UV) and near UV light to give yellow PL emission and LLP. The emission origins from the d-f transition of Eu2+. The results of thermal glow curve indicate that the LLP is originated from the trap level with depth of 0.83 eV in the forbidden band of glass host. This study is beneficial for finding other rare earth ions activated luminescent glasses for white light LEDs.
In this article, a new Eu2+ ion activated silicate glass was prepared. The glass composition is 2CaO-MgO-3SiO2-0.015Eu2O3(CMSE). The transmitted spectrum, steady-state photoluminescence(PL) spectrum, long-lasting phosphorescence(LLP) and thermal glow were performed to investigate the luminescent properties of the CMSE sample. It was found that the CMSE sample can be excited by ultraviolet(UV) and near UV light to give yellow PL emission and LLP. The emission origins from the d-f transition of Eu2+. The results of thermal glow curve indicate that the LLP is originated from the trap level with depth of 0.83 eV in the forbidden band of glass host. This study is beneficial for finding other rare earth ions activated luminescent glasses for white light LEDs.
2016, 33(1): 70-75
doi: 10.11944/j.issn.1000-0518.2016.01.150208
Abstract:
Zinc and cobolt ethylenediaminetriacetates[M(H2O)6] [M(ED3A)(H2O)]2·2H2O[M=Zn(1), Co(2); H3ED3A=ethylenediaminetriacetic acid, C8H14N2O6] were obtained on the hydrothermal conditions at 140℃ in a weak acidic solution. Complexes 1 and 2 were characterized by elemental analysis, IR, TG-DTG, solution 13C NMR spectroscopy, and X-ray analysis. ED3A coordinates with zinc or cobalt ions as a pentadentate ligand. The metal ions are arranged in octahedral coordination geometries[MN2O4] or [MO6]. Comparisons of 13C NMR spectra demonstrate that the coordination of ED3A zinc complex is stable in weak acidic solution(pH 3~7), while ED3A cyclizes to form ketopiperazinediacetic acid (H2kpda, C8H12N2O5) under acidic condition.
Zinc and cobolt ethylenediaminetriacetates[M(H2O)6] [M(ED3A)(H2O)]2·2H2O[M=Zn(1), Co(2); H3ED3A=ethylenediaminetriacetic acid, C8H14N2O6] were obtained on the hydrothermal conditions at 140℃ in a weak acidic solution. Complexes 1 and 2 were characterized by elemental analysis, IR, TG-DTG, solution 13C NMR spectroscopy, and X-ray analysis. ED3A coordinates with zinc or cobalt ions as a pentadentate ligand. The metal ions are arranged in octahedral coordination geometries[MN2O4] or [MO6]. Comparisons of 13C NMR spectra demonstrate that the coordination of ED3A zinc complex is stable in weak acidic solution(pH 3~7), while ED3A cyclizes to form ketopiperazinediacetic acid (H2kpda, C8H12N2O5) under acidic condition.
2016, 33(1): 76-83
doi: 10.11944/j.issn.1000-0518.2016.01.150199
Abstract:
A new Keggin-type polyoxometalate-based silver compound constructed from a semi-rigid bis-pyridyl-bis-amide ligand 3-bpcd(N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide), {[Ag2(3-bpcd)3] [Ag(3-bpcd)(SiMo12O40)]2(3-H2bpcd)2}·7H2O was prepared under the hydrothermal condition and characterized by IR, element analysis and X-ray single-crystal diffraction. The title complex is a triclinic system with space group P-1, whose cell parameters are a=1.3597(5) nm, b=1.4949(5) nm, c=2.5249(10) nm, α=88.998(6)°, β=88.856(7)°, γ=67.458(6)°, V=4.739(3) nm3, Mr=6471.02, Dc=2.261g/cm3, Z=1, S=0.955, F(000)=3124, R1=0.0768, wR2=0.1936. In this compound, a[Ag(3-bpcd)(SiMo12O40)]26- one-dimensional chain, a dinuclear[Ag2(3-bpcd)3]2+ structure unit and two non-coordinated protonated organic ligands 3-bpcd coexists. These structural units are extended into the three-dimensional supramolecular network by the hydrogen bonding interactions. The title complex modified carbon paste electrode displays good electrocatalytic activity toward NO2- reduction. Additionally, this complex possesses a remarkable photocatalytic ability for the degradation of Rhodamine B(RhB) dye. CCDC:1401875.
A new Keggin-type polyoxometalate-based silver compound constructed from a semi-rigid bis-pyridyl-bis-amide ligand 3-bpcd(N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide), {[Ag2(3-bpcd)3] [Ag(3-bpcd)(SiMo12O40)]2(3-H2bpcd)2}·7H2O was prepared under the hydrothermal condition and characterized by IR, element analysis and X-ray single-crystal diffraction. The title complex is a triclinic system with space group P-1, whose cell parameters are a=1.3597(5) nm, b=1.4949(5) nm, c=2.5249(10) nm, α=88.998(6)°, β=88.856(7)°, γ=67.458(6)°, V=4.739(3) nm3, Mr=6471.02, Dc=2.261g/cm3, Z=1, S=0.955, F(000)=3124, R1=0.0768, wR2=0.1936. In this compound, a[Ag(3-bpcd)(SiMo12O40)]26- one-dimensional chain, a dinuclear[Ag2(3-bpcd)3]2+ structure unit and two non-coordinated protonated organic ligands 3-bpcd coexists. These structural units are extended into the three-dimensional supramolecular network by the hydrogen bonding interactions. The title complex modified carbon paste electrode displays good electrocatalytic activity toward NO2- reduction. Additionally, this complex possesses a remarkable photocatalytic ability for the degradation of Rhodamine B(RhB) dye. CCDC:1401875.
2016, 33(1): 84-91
doi: 10.11944/j.issn.1000-0518.2016.01.150149
Abstract:
Ethylene glycol(EG) intercalated layered double hydroxide(LDH) can be used as an interlayer catalytic reactor for the esterification of naphthenic acids with EG in oil. However, long synthesis time for EG intercalated LDH limits its further application. In the present investigation, EG intercalated NiAl-LDH was synthesized via a microwave-assisted ion exchange method by the aid of KOH and with nitrate LDH as precursor. The effects of microwave irradiating time and power, and the reaction temperature on the structure of EG intercalated LDH were investigated. XRD, FT-IR and TG-DSC were used to characterize EG intercalated LDHs prepared. Microwave irradiation was found to provide sufficient energy to accelerate the diffusion of exchanging anions into the interlayer and weaken the interaction between the layers and original interlayer anions. As a result, well-crystallized EG intercalated LDH can be synthesized under 550 W microwave irradiation at 120℃ for 10 min. The EG intercalated LDH prepared shows similar structure and properties and higher crystallinity as that prepared by conventional method, while the preparation time can be significantly reduced from 12 h to 10 min.
Ethylene glycol(EG) intercalated layered double hydroxide(LDH) can be used as an interlayer catalytic reactor for the esterification of naphthenic acids with EG in oil. However, long synthesis time for EG intercalated LDH limits its further application. In the present investigation, EG intercalated NiAl-LDH was synthesized via a microwave-assisted ion exchange method by the aid of KOH and with nitrate LDH as precursor. The effects of microwave irradiating time and power, and the reaction temperature on the structure of EG intercalated LDH were investigated. XRD, FT-IR and TG-DSC were used to characterize EG intercalated LDHs prepared. Microwave irradiation was found to provide sufficient energy to accelerate the diffusion of exchanging anions into the interlayer and weaken the interaction between the layers and original interlayer anions. As a result, well-crystallized EG intercalated LDH can be synthesized under 550 W microwave irradiation at 120℃ for 10 min. The EG intercalated LDH prepared shows similar structure and properties and higher crystallinity as that prepared by conventional method, while the preparation time can be significantly reduced from 12 h to 10 min.
2016, 33(1): 92-97
doi: 10.11944/j.issn.1000-0518.2016.01.150224
Abstract:
In this paper, a kind of polyaniline/attapulgite(PANI/ATP)-supported nano sized zero valence iron(nZVI) composites were synthesized by the liquid-phase chemical reduction method. The as-prepared nZVI/PANI/ATP nanocomposites were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray photoelectron energy spectrum analyzer(XPS). The effects of the degradation time and pH on the adsorption of methyl orange on synthetic materials were investigated. Kinetic analysis and degradation mechanism were discussed. The results show that the nZVI/PANI/ATP composites can effectively degrade methyl orange over a wide range of pH and keep degradation activity in a long storage term. It is shown that more than 95.8% of methyl orange with an initial concentration of 20 mg/L and volume of 50 mL is removed from the aqueous solution after 30 min when the catalysts amount is 1 g/L. The process of the degradation of methyl orange was well described by the pseudo-second order reaction kinetics.
In this paper, a kind of polyaniline/attapulgite(PANI/ATP)-supported nano sized zero valence iron(nZVI) composites were synthesized by the liquid-phase chemical reduction method. The as-prepared nZVI/PANI/ATP nanocomposites were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray photoelectron energy spectrum analyzer(XPS). The effects of the degradation time and pH on the adsorption of methyl orange on synthetic materials were investigated. Kinetic analysis and degradation mechanism were discussed. The results show that the nZVI/PANI/ATP composites can effectively degrade methyl orange over a wide range of pH and keep degradation activity in a long storage term. It is shown that more than 95.8% of methyl orange with an initial concentration of 20 mg/L and volume of 50 mL is removed from the aqueous solution after 30 min when the catalysts amount is 1 g/L. The process of the degradation of methyl orange was well described by the pseudo-second order reaction kinetics.
2016, 33(1): 98-102
doi: 10.11944/j.issn.1000-0518.2016.01.150195
Abstract:
Polythiophene(PTH)/Polypyrrole(PPY)/TiO2 conductive polymer composites materials were prepared by chemical solid-phase oxidation reaction in the presence of TiO2 nanoparticles and ferric chloride at room temperature. X-ray crystallography(XRD), scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FT-IR), thermogravimetric analysis(TG) and electrochemical impedance spectroscopy(EIS) were employed to characterize the morphology, thermal stability and anti-corrosion properties of the composites with different dopping amounts of nano-TiO2. PTH/PPy/6% TiO2 conductive polymer film at the application temperature(20~300℃) meets the anti-corrosion requirements to prevent the stainless steel corrosion with a 0.8 V potential higher than the free corrosion potential of bare stainless steel, while the corrosion current densities are lower two orders of magnitude. Nano-TiO2 improves the anode protection and the anti-corrosion properties of the PTH/PPY material. Furthermore, nano-TiO2 bends the polymer tightly to increase the mechanical properties of the composites by reducing membrane defects.
Polythiophene(PTH)/Polypyrrole(PPY)/TiO2 conductive polymer composites materials were prepared by chemical solid-phase oxidation reaction in the presence of TiO2 nanoparticles and ferric chloride at room temperature. X-ray crystallography(XRD), scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FT-IR), thermogravimetric analysis(TG) and electrochemical impedance spectroscopy(EIS) were employed to characterize the morphology, thermal stability and anti-corrosion properties of the composites with different dopping amounts of nano-TiO2. PTH/PPy/6% TiO2 conductive polymer film at the application temperature(20~300℃) meets the anti-corrosion requirements to prevent the stainless steel corrosion with a 0.8 V potential higher than the free corrosion potential of bare stainless steel, while the corrosion current densities are lower two orders of magnitude. Nano-TiO2 improves the anode protection and the anti-corrosion properties of the PTH/PPY material. Furthermore, nano-TiO2 bends the polymer tightly to increase the mechanical properties of the composites by reducing membrane defects.
2016, 33(1): 103-107
doi: 10.11944/j.issn.1000-0518.2016.01.150390
Abstract:
A graphene modified glassy carbon electrode(GN/GCE) was prepared. The electrochemical behavior of metol at the modified electrode was investigated in 0.5 mol/L HAc-NaAc(pH=4.8) buffer solution by cyclic voltammetry(CV) and square wave voltammetry(SWV), and a novel method for the determination of metol was established. The results show that the redox peak potential difference of metol on GN/GCE is smaller than that on the bare GCE, while the peak current is significantly increased, indicating that the GN/GCE has electrocatalytic activity toward the redox of metol. A linear dependence of the reduction current versus the metol concentration using SWV is obtained in the range of 8.0×10-8~5.0×10-5 mol/L, with a detection limit of 2.0×10-8 mol/L. The concomitant hydroquinone affects on the detection of metol, but the interference can be eliminated by using the SWV method. The proposed method can be used to determine metol in photographic imaging agents.
A graphene modified glassy carbon electrode(GN/GCE) was prepared. The electrochemical behavior of metol at the modified electrode was investigated in 0.5 mol/L HAc-NaAc(pH=4.8) buffer solution by cyclic voltammetry(CV) and square wave voltammetry(SWV), and a novel method for the determination of metol was established. The results show that the redox peak potential difference of metol on GN/GCE is smaller than that on the bare GCE, while the peak current is significantly increased, indicating that the GN/GCE has electrocatalytic activity toward the redox of metol. A linear dependence of the reduction current versus the metol concentration using SWV is obtained in the range of 8.0×10-8~5.0×10-5 mol/L, with a detection limit of 2.0×10-8 mol/L. The concomitant hydroquinone affects on the detection of metol, but the interference can be eliminated by using the SWV method. The proposed method can be used to determine metol in photographic imaging agents.
2016, 33(1): 108-115
doi: 10.11944/j.issn.1000-0518.2016.01.150214
Abstract:
We synthesize a novel sensing molecule 1-hydroxy-naphthalen-ethyl-3-hydroxy-naphthalen-methyl-benzoimidazo-bromate(J1) which can carry out a single selective colorimetric dual-channel recognition of CN- in aqueous medium. When F-, Cl-, Br-, I-, AcO-, HSO4-, ClO4-, H2PO4-, SCN- and CN- ions were added respectively in sensing molecule J1's DMSO/H2O(3:2 volume ratio) HEPES(pH=7.2) solution, only CN- turns the solution from colorless to deep yellow. In the same time, only CN- among the ions added in sensing molecule J1's DMSO/H2O(4:1, volume ratio) HEPES(pH=7.2) solution allows the chemosensor responding with a dramatic color change, from colorless to bright yellow. These recognition processes are not disturbed by other negative ions. This indicates that sensing molecule J1 is a good colorimetric recognition receptor of CN-. The UV-Vis spectrum of sensing molecule J1 has a wide linear range over CN- concentration from 3.875×10-4 mol/L to 2.15×10-2 mol/L with a detection limit of 1.575×10-7 mol/L. The linear range of the fluorescence of the sensor for CN- is at the concentration from 0.8×10-4 mol/L to 1.60×10-3 mol/L with a detection limit of 4.63×10-6 mol/L. The sensing molecule J1 has good selection, high sensitivity and strong antidisturbance on CN- in aqueous medium. Based on sensing molecule J1's high selection on CN-, we specially prepare test paper which can test CN- in water in a convenient, fast and accurate way.
We synthesize a novel sensing molecule 1-hydroxy-naphthalen-ethyl-3-hydroxy-naphthalen-methyl-benzoimidazo-bromate(J1) which can carry out a single selective colorimetric dual-channel recognition of CN- in aqueous medium. When F-, Cl-, Br-, I-, AcO-, HSO4-, ClO4-, H2PO4-, SCN- and CN- ions were added respectively in sensing molecule J1's DMSO/H2O(3:2 volume ratio) HEPES(pH=7.2) solution, only CN- turns the solution from colorless to deep yellow. In the same time, only CN- among the ions added in sensing molecule J1's DMSO/H2O(4:1, volume ratio) HEPES(pH=7.2) solution allows the chemosensor responding with a dramatic color change, from colorless to bright yellow. These recognition processes are not disturbed by other negative ions. This indicates that sensing molecule J1 is a good colorimetric recognition receptor of CN-. The UV-Vis spectrum of sensing molecule J1 has a wide linear range over CN- concentration from 3.875×10-4 mol/L to 2.15×10-2 mol/L with a detection limit of 1.575×10-7 mol/L. The linear range of the fluorescence of the sensor for CN- is at the concentration from 0.8×10-4 mol/L to 1.60×10-3 mol/L with a detection limit of 4.63×10-6 mol/L. The sensing molecule J1 has good selection, high sensitivity and strong antidisturbance on CN- in aqueous medium. Based on sensing molecule J1's high selection on CN-, we specially prepare test paper which can test CN- in water in a convenient, fast and accurate way.
2016, 33(1): 116-122
doi: 10.11944/j.issn.1000-0518.2016.01.150239
Abstract:
Poly(thionine)/multi-walled carbon nanotubes(p-Th/MWNTs) photoelectrode was prepared by electropolymerizing thionine(Th) on the surface of MWNTs-modified ITO electrode. A novel photoelectrochemical bile acid sensor was fabricated by immobilizing 3α-hydroxysteroid dehydrogenase(3α-HSD) on the surface of the photoelectrode. With this photoelectrode as an electron acceptor, and nicotinamide adenine dinucleotide(NADH) from enzymatic reaction as an electron donor, bile acid was determined by the photocurrent from photoelectrochemical effect between p-Th on the photoelectrode and NADH produced in 3α-HSD catalyzed reaction of bile acid. The preparing condition of the photoelectrode, such as MWNTs coating amount, initial concentration of Th and the enzyme loading were optimized. The effects of the electrolyte pH, the concentration of NAD+ and the bias voltage on detecting the substrate were investigated at optimized conditions. The measuring range of bile acid sensor is from 1.80 to 40.0 μmol/L with a sensitivity of 5.86 μA/(mol·L), and the detection limit is estimated to be 0.67 μmol/L. The recovery is in the range of 96%~104% for the determination of cholic acid in sodinm cholate tablets and bile acid in human urine.
Poly(thionine)/multi-walled carbon nanotubes(p-Th/MWNTs) photoelectrode was prepared by electropolymerizing thionine(Th) on the surface of MWNTs-modified ITO electrode. A novel photoelectrochemical bile acid sensor was fabricated by immobilizing 3α-hydroxysteroid dehydrogenase(3α-HSD) on the surface of the photoelectrode. With this photoelectrode as an electron acceptor, and nicotinamide adenine dinucleotide(NADH) from enzymatic reaction as an electron donor, bile acid was determined by the photocurrent from photoelectrochemical effect between p-Th on the photoelectrode and NADH produced in 3α-HSD catalyzed reaction of bile acid. The preparing condition of the photoelectrode, such as MWNTs coating amount, initial concentration of Th and the enzyme loading were optimized. The effects of the electrolyte pH, the concentration of NAD+ and the bias voltage on detecting the substrate were investigated at optimized conditions. The measuring range of bile acid sensor is from 1.80 to 40.0 μmol/L with a sensitivity of 5.86 μA/(mol·L), and the detection limit is estimated to be 0.67 μmol/L. The recovery is in the range of 96%~104% for the determination of cholic acid in sodinm cholate tablets and bile acid in human urine.
