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2012 Volume 29 Issue 9
2012, 29(9): 977-984
doi: 10.3724/SP.J.1095.2012.20079
Abstract:
Functional organic nanomaterials have attracted extensive attention as molecular electronic devices.Porphyrin compounds have demonstrated novel optoelectronic property and thermal stability due to their special π-electronic system and conjugated delocalized structure,and they have good prospect as optoelectronic devices,mimic enzyme,molecular recognition and sensors.Moreover,porphyrin compounds are often used as building block to build functional optoelectronic materials,based on readily modified planar molecular structures.In this paper,the characteristics and application progress of porphyrin compounds in optoelectronic devices are reviewed.
Functional organic nanomaterials have attracted extensive attention as molecular electronic devices.Porphyrin compounds have demonstrated novel optoelectronic property and thermal stability due to their special π-electronic system and conjugated delocalized structure,and they have good prospect as optoelectronic devices,mimic enzyme,molecular recognition and sensors.Moreover,porphyrin compounds are often used as building block to build functional optoelectronic materials,based on readily modified planar molecular structures.In this paper,the characteristics and application progress of porphyrin compounds in optoelectronic devices are reviewed.
2012, 29(9): 985-989
doi: 10.3724/SP.J.1095.2012.00474
Abstract:
Double metal cyanide/rare earth metal complex was used to catalyze the copolymerization between propylene oxide and carbon dioxide.It was found that the catalytic activity was much higher than that using rare earth ternary catalyst alone.The method could produce resultant polymer with average relative molecular mass above 1.0×105 using the as-prepared catalyst with less than 2% propylene carbonate by product,which was remarkably decreased from over 10% mass fraction using the rare earth ternary catalyst alone.The effects of complex catalyst component,including the category of rare earth metal,the molar ratio of n(Y)/n(Zn),the acidity of the ligand of rare earth metal salt,as well as the reaction pressure and reaction time on the copolymerization were investigated.It was found that Y(CCl3COO)3 could improve catalytic activity of double metal cyanide,when n(Y)/n(Zn)=6 and reaction time was 4 h,compared with the double metal cyanide,the catalytic activity was increased by 31.5% while the carbonate unit content in the polymer was reduced.Our results indicate that the rare earth metal complexes only activated the complexation of propylene oxide,and the catalytic process still followed that of the double metal cyanide complex.
Double metal cyanide/rare earth metal complex was used to catalyze the copolymerization between propylene oxide and carbon dioxide.It was found that the catalytic activity was much higher than that using rare earth ternary catalyst alone.The method could produce resultant polymer with average relative molecular mass above 1.0×105 using the as-prepared catalyst with less than 2% propylene carbonate by product,which was remarkably decreased from over 10% mass fraction using the rare earth ternary catalyst alone.The effects of complex catalyst component,including the category of rare earth metal,the molar ratio of n(Y)/n(Zn),the acidity of the ligand of rare earth metal salt,as well as the reaction pressure and reaction time on the copolymerization were investigated.It was found that Y(CCl3COO)3 could improve catalytic activity of double metal cyanide,when n(Y)/n(Zn)=6 and reaction time was 4 h,compared with the double metal cyanide,the catalytic activity was increased by 31.5% while the carbonate unit content in the polymer was reduced.Our results indicate that the rare earth metal complexes only activated the complexation of propylene oxide,and the catalytic process still followed that of the double metal cyanide complex.
2012, 29(9): 990-994
doi: 10.3724/SP.J.1095.2012.00498
Abstract:
An homopolymer and acrylonitrile/itaconic acid(AN/IA) bipolymer and AN/IA/MA(methacrylate) terpolymer were prepared in ethylene carbonate(EC) solution using azodiisobutyronitrile(AIBN) as initiator via the free radical solution polymerization method.Effect of reaction temperature on AN homopolymerization and effect of monomer concentration on the copolymerization were investigated.AN copolymer with a relative molecular mass of 4.5×105 and monomer conversion of 85% was synthesized.Relative molecular masses of AN homopolymer,AN/IA and AN/IA/MA copolymers were controlled through N-formylpiperidine(FP) and 1-dodecanethiol(DDT) as chain transfer agents.Influence of the mass fraction of chain transfer agents on the molecular mass and conversion rate of the copolymers were also studied.The results shows that a polymer with molecular mass of 1×105 and monomer conversion of 80% was obtained by 0.25% mass fraction of DDT as chain transfer agent.s
An homopolymer and acrylonitrile/itaconic acid(AN/IA) bipolymer and AN/IA/MA(methacrylate) terpolymer were prepared in ethylene carbonate(EC) solution using azodiisobutyronitrile(AIBN) as initiator via the free radical solution polymerization method.Effect of reaction temperature on AN homopolymerization and effect of monomer concentration on the copolymerization were investigated.AN copolymer with a relative molecular mass of 4.5×105 and monomer conversion of 85% was synthesized.Relative molecular masses of AN homopolymer,AN/IA and AN/IA/MA copolymers were controlled through N-formylpiperidine(FP) and 1-dodecanethiol(DDT) as chain transfer agents.Influence of the mass fraction of chain transfer agents on the molecular mass and conversion rate of the copolymers were also studied.The results shows that a polymer with molecular mass of 1×105 and monomer conversion of 80% was obtained by 0.25% mass fraction of DDT as chain transfer agent.s
2012, 29(9): 995-999
doi: 10.3724/SP.J.1095.2012.00456
Abstract:
Porous β-tricalcium phosphate/chitosan/polyvinyl alcohol(β-TCP/CS/PVA) composite hydrogel was prepared successfully by the freezing-thawing method using NaCl as porogen.The effects of different mass ratio of CS to β-TCP on the crystallinity of PVA and the performance of target β-TCP/CS/PVA composite hydrogel has been studied.The products were characterized by means of XRD,SEM,TG-DTA and their water uptake,swelling ratio,and tensile strength were also determined and compared.The water uptake of the hydrogel composite was about 70%~76%(mass fraction).When the mass ratio of CS to β-TCP was 2:8,it exhibited good mechanical properties:tensile strength of 0.56 MPa and elongation at breakage of 370% which can withstand normal human eye pressure.Therefore,the porous β-TCP/CS/PVA hydrogel composite is promising to be used as the skirt for artificial cornea.
Porous β-tricalcium phosphate/chitosan/polyvinyl alcohol(β-TCP/CS/PVA) composite hydrogel was prepared successfully by the freezing-thawing method using NaCl as porogen.The effects of different mass ratio of CS to β-TCP on the crystallinity of PVA and the performance of target β-TCP/CS/PVA composite hydrogel has been studied.The products were characterized by means of XRD,SEM,TG-DTA and their water uptake,swelling ratio,and tensile strength were also determined and compared.The water uptake of the hydrogel composite was about 70%~76%(mass fraction).When the mass ratio of CS to β-TCP was 2:8,it exhibited good mechanical properties:tensile strength of 0.56 MPa and elongation at breakage of 370% which can withstand normal human eye pressure.Therefore,the porous β-TCP/CS/PVA hydrogel composite is promising to be used as the skirt for artificial cornea.
2012, 29(9): 1000-1005
doi: 10.3724/SP.J.1095.2012.00481
Abstract:
Three new quinazoline derivatives 5a~5c bearing piperazine have been designed and synthesized by four-step reactions of cyclization,chlorination,substitution and condensation using 2-amino-5-chlorobenzoic acid and formamide as starting materials.Their structures were confirmed by 1H NMR,13C NMR,ESI-MS and IR.The in vitro cytotoxicities against SGC-7901(human gastric cancer),KB(human oral epidermoid cancer) and HT-1080(human fibrosarcoma) cell lines of compounds 5a~5c were tested with colorimetric MTT assay.The results indicated that compounds 5a~5c had poor anticancer activities against SGC-7901 and HT-1080 cell lines,while had no notable inhibitory activity against KB cell lines.
Three new quinazoline derivatives 5a~5c bearing piperazine have been designed and synthesized by four-step reactions of cyclization,chlorination,substitution and condensation using 2-amino-5-chlorobenzoic acid and formamide as starting materials.Their structures were confirmed by 1H NMR,13C NMR,ESI-MS and IR.The in vitro cytotoxicities against SGC-7901(human gastric cancer),KB(human oral epidermoid cancer) and HT-1080(human fibrosarcoma) cell lines of compounds 5a~5c were tested with colorimetric MTT assay.The results indicated that compounds 5a~5c had poor anticancer activities against SGC-7901 and HT-1080 cell lines,while had no notable inhibitory activity against KB cell lines.
2012, 29(9): 1006-1010
doi: 10.3724/SP.J.1095.2012.00417
Abstract:
Cinchona alkaloid-9-O-trimethylsilyl(TMS) derivatives have been used to catalyze the asymmetric "interrupted" Feist-Bénary reaction of ethyl bromopyruvate/substituted bromo-ketoesters with 1,3-cyclohexadione.The corresponding hydroxydihydrofurans have been obtained in excellent yields(85%~97%) and with up to 90% ee value.
Cinchona alkaloid-9-O-trimethylsilyl(TMS) derivatives have been used to catalyze the asymmetric "interrupted" Feist-Bénary reaction of ethyl bromopyruvate/substituted bromo-ketoesters with 1,3-cyclohexadione.The corresponding hydroxydihydrofurans have been obtained in excellent yields(85%~97%) and with up to 90% ee value.
2012, 29(9): 1011-1016
doi: 10.3724/SP.J.1095.2012.20146
Abstract:
A facile synthesis of substituted pyridin-4(1H)-ones from readily available α-(i>N,N-dimethylamino)-alkenoyl ketene-S,S-acetals and aliphatic amines has been developed.Substituted pyridin4(1H)-ones were synthesized via a formal[5C+1N]annulation of α-(N,N-dimethylamino)-alkenoyl keteneS,S-acetals in N,N-dimethylformamide at 60℃.An intramolecular aza-nucleophilic vinyl substitution reaction occurs to give the corresponding pyridin-4(1H)-ones in high yields(75%~95%).
A facile synthesis of substituted pyridin-4(1H)-ones from readily available α-(i>N,N-dimethylamino)-alkenoyl ketene-S,S-acetals and aliphatic amines has been developed.Substituted pyridin4(1H)-ones were synthesized via a formal[5C+1N]annulation of α-(N,N-dimethylamino)-alkenoyl keteneS,S-acetals in N,N-dimethylformamide at 60℃.An intramolecular aza-nucleophilic vinyl substitution reaction occurs to give the corresponding pyridin-4(1H)-ones in high yields(75%~95%).
2012, 29(9): 1017-1022
doi: 10.3724/SP.J.1095.2012.00444
Abstract:
The liquid-phase selective oxidation of ethylbenzene to acetophenone by oxygen using MnO4- exchanged Mg-Al-hydrotalcite as catalyst has been investigated in the absence of solvent.The effects of catalyst dosage,reaction temperature and reaction time on the yield of acetophenone and the conversion of ethylbenzene have been studied.Under the following optimized conditions:catalyst 3 g,ethylbenzene 45 mL,reaction temperature 120℃,the oxygen flow velocity 100 mL/min,the yield and selectivity of acetophenone can be up to 57.0% and 96.3%,respectively.The catalyst retained high catalytic activity after three recylclings.
The liquid-phase selective oxidation of ethylbenzene to acetophenone by oxygen using MnO4- exchanged Mg-Al-hydrotalcite as catalyst has been investigated in the absence of solvent.The effects of catalyst dosage,reaction temperature and reaction time on the yield of acetophenone and the conversion of ethylbenzene have been studied.Under the following optimized conditions:catalyst 3 g,ethylbenzene 45 mL,reaction temperature 120℃,the oxygen flow velocity 100 mL/min,the yield and selectivity of acetophenone can be up to 57.0% and 96.3%,respectively.The catalyst retained high catalytic activity after three recylclings.
2012, 29(9): 1023-1029
doi: 10.3724/SP.J.1095.2012.00479
Abstract:
The photocatalytic degradation of 2,4-dichlorophenol was carried out using un-doped and nitrogen-doped bismuth oxide as catalysts under visible-light irradiation.The results indicated that the nitrogen-doped bismuth oxide exhibited a higher photocatalytic activity than that of the un-doped bismuth oxide.When 2.0 g/L of nitrogen-doped bismuth oxide was added to 20 mg/L of 2,4-dichlorophenol aqueous solution with initial pH=7,the degradation rate could reach 91.5%.Moreover,the relationship between 2,4-dichlorophenol degradation rate and its initial concentration follows the Langmuir-Hinshelwood model.The variations of total organic carbon and Cl- were also inspected during the photocatalytic reaction.It is suggested that it is beneficial for the mineralization and dechlorination for 2,4-dichlorophenol by using nitrogen-doped bismuth oxide as photocatalyst.
The photocatalytic degradation of 2,4-dichlorophenol was carried out using un-doped and nitrogen-doped bismuth oxide as catalysts under visible-light irradiation.The results indicated that the nitrogen-doped bismuth oxide exhibited a higher photocatalytic activity than that of the un-doped bismuth oxide.When 2.0 g/L of nitrogen-doped bismuth oxide was added to 20 mg/L of 2,4-dichlorophenol aqueous solution with initial pH=7,the degradation rate could reach 91.5%.Moreover,the relationship between 2,4-dichlorophenol degradation rate and its initial concentration follows the Langmuir-Hinshelwood model.The variations of total organic carbon and Cl- were also inspected during the photocatalytic reaction.It is suggested that it is beneficial for the mineralization and dechlorination for 2,4-dichlorophenol by using nitrogen-doped bismuth oxide as photocatalyst.
2012, 29(9): 1030-1035
doi: 10.3724/SP.J.1095.2012.00480
Abstract:
Using Keggin-type copper-substituted heteropolyanion PW11O39Cu(Ⅱ)(H2O)5-(PW11Cu) as a visible photocatalyst,and organic dye Rhodamine B(RhB) as a model pollutant,this work reports a study on the visible photocatalysis of PW11Cu towards RhB degradation in aqueous solution under visible light irradiation.A visible photocatalysis mechanism is proposed.At the same time,influences of the initial RhB concentration,the initial PW11Cu concentration and the solution pH on the degradation rate of RhB are also examined.Experimental results show that 100% of RhB degradation is reached at 80 min under visible light irradiation of a solution containing 15.6 μmol/L PW11Cu and 10 μmol/L RhB,and a total organic carbon removal is about 33%.The visible photocatalytic degradation of RhB follows the quasi-first order kinetic regime and the observed rate constant is estimated to be 3.1×10-2,2.0×10-2 and 1.5×10-2 min-1 corresponding to the initial RhB concentration of 20,30 and 40 μmol/L,respectively.
Using Keggin-type copper-substituted heteropolyanion PW11O39Cu(Ⅱ)(H2O)5-(PW11Cu) as a visible photocatalyst,and organic dye Rhodamine B(RhB) as a model pollutant,this work reports a study on the visible photocatalysis of PW11Cu towards RhB degradation in aqueous solution under visible light irradiation.A visible photocatalysis mechanism is proposed.At the same time,influences of the initial RhB concentration,the initial PW11Cu concentration and the solution pH on the degradation rate of RhB are also examined.Experimental results show that 100% of RhB degradation is reached at 80 min under visible light irradiation of a solution containing 15.6 μmol/L PW11Cu and 10 μmol/L RhB,and a total organic carbon removal is about 33%.The visible photocatalytic degradation of RhB follows the quasi-first order kinetic regime and the observed rate constant is estimated to be 3.1×10-2,2.0×10-2 and 1.5×10-2 min-1 corresponding to the initial RhB concentration of 20,30 and 40 μmol/L,respectively.
2012, 29(9): 1036-1040
doi: 10.3724/SP.J.1095.2012.00477
Abstract:
Colloidal precursors were synthesized by precipitation method using zinc acetate(ZnAc2) and sodium hydroxide(NaOH) aqueous solution at room temperature.The products of Zn5(OH)8(Ac)2·2H2O and ZnO were prepared by controlling the pH values of the reaction system.The composition,structure,and morphology of the resultant soild were characterized by using X-ray diffraction,scanning electron microscopy and energy dispersive spectrometer.We found that when the pH value of the precursor solution was 7,a steady colloid could be synthesized by the precipitation method,and the composition of the product was Zn5(OH)8(Ac)2·2H2O after dried at room temperature.If the pH value was 14,the coagulation phenomenon occurred with the ageing of colloidal precursor,and the coagulation product was hexagonal flake ZnO.In addition,the growth mechanism of ZnO nanomaterials was discussed,and it was also considered from the effects of pH value on the stability of colloidal precursor.
Colloidal precursors were synthesized by precipitation method using zinc acetate(ZnAc2) and sodium hydroxide(NaOH) aqueous solution at room temperature.The products of Zn5(OH)8(Ac)2·2H2O and ZnO were prepared by controlling the pH values of the reaction system.The composition,structure,and morphology of the resultant soild were characterized by using X-ray diffraction,scanning electron microscopy and energy dispersive spectrometer.We found that when the pH value of the precursor solution was 7,a steady colloid could be synthesized by the precipitation method,and the composition of the product was Zn5(OH)8(Ac)2·2H2O after dried at room temperature.If the pH value was 14,the coagulation phenomenon occurred with the ageing of colloidal precursor,and the coagulation product was hexagonal flake ZnO.In addition,the growth mechanism of ZnO nanomaterials was discussed,and it was also considered from the effects of pH value on the stability of colloidal precursor.
2012, 29(9): 1041-1045
doi: 10.3724/SP.J.1095.2012.00426
Abstract:
We investigated the effect of boric acid on the crystallization of L-lysine monohydrochloride dihydrate on self-assembled monolayer(SAM) of L-cysteine.SAM of L-cysteine was employed to induce the crystallization of L-lysine monohydrochloride dehydrate(LMH).It was found that the crystals of LMH grew preferentially in solution rather than on the SAM.That the SAM did not promote but inhibit the nucleation of LMH was found firstly in the research field of inducing crystals by SAM.This unusual result may largely due to the repulsion between the positive charges of the LMH and L-cysteine.The LMH-boric acid(n(LMH):n(H3BO3)=1:1) system was introduced to study further.The XRD results showed that diffraction peaks at 14.9° and 27.9° corresponding to the lattice plane of(101) and(112) appeared first.It means that boric acid prefer to grow on the SAM of L-cysteine.Then the LMH crystallization was improved remarkably after the crystallization of boric acid.After 24 h,we obtained diffraction peaks corresponding to the LMH lattice plane of(101) and(112).The SEM results showed that the appearance of the LMH crystal also changed greatly,from massive on the SAM to needle form on boric acid crystals.The above results demonstrated that boric acid could be used to accelerate the growth speed of LMH and affect its crystal morphology significantly.
We investigated the effect of boric acid on the crystallization of L-lysine monohydrochloride dihydrate on self-assembled monolayer(SAM) of L-cysteine.SAM of L-cysteine was employed to induce the crystallization of L-lysine monohydrochloride dehydrate(LMH).It was found that the crystals of LMH grew preferentially in solution rather than on the SAM.That the SAM did not promote but inhibit the nucleation of LMH was found firstly in the research field of inducing crystals by SAM.This unusual result may largely due to the repulsion between the positive charges of the LMH and L-cysteine.The LMH-boric acid(n(LMH):n(H3BO3)=1:1) system was introduced to study further.The XRD results showed that diffraction peaks at 14.9° and 27.9° corresponding to the lattice plane of(101) and(112) appeared first.It means that boric acid prefer to grow on the SAM of L-cysteine.Then the LMH crystallization was improved remarkably after the crystallization of boric acid.After 24 h,we obtained diffraction peaks corresponding to the LMH lattice plane of(101) and(112).The SEM results showed that the appearance of the LMH crystal also changed greatly,from massive on the SAM to needle form on boric acid crystals.The above results demonstrated that boric acid could be used to accelerate the growth speed of LMH and affect its crystal morphology significantly.
2012, 29(9): 1046-1052
doi: 10.3724/SP.J.1095.2012.00429
Abstract:
With benzoyl peroxide as initiator,a series of styrene-maleic anhydride copolymer was prepared by solution copolymerization under different temperatures.Polystyrene-maleic anhydride sulfonic acid sodium(SSMA) with different relative molecular mass was obtained by sulfonated the polystyrene-maleic anhdride.The dispersibility of 20% diflubenzuron suspension concentrate was identified by assaying and analyzing the diameter of particles,Zeta potentials and viscosities.The results showed that the optimal dispersant was SSMA,which was prepared at 75℃,and the most suitable concentration was 3%.At pH=9,the dispersion stability of suspension concentrate was the best due to the strong steric hindrance provided by completely ionizing of the molecules.Na+ or Ca2+ was able to decrease the absolute value of Zeta potential by compressing the electronic double layer thickness of particles surface,which could lead to particles aggregation due to the reduction of electric quantity and ultimately deteriorate the dispersive effect of suspension concentrate.If the ions concentration were the same,the coagulation capacity by Ca2+ was stronger than that of Na+,and the dispersion stability of suspension was worse after adding Ca2+.
With benzoyl peroxide as initiator,a series of styrene-maleic anhydride copolymer was prepared by solution copolymerization under different temperatures.Polystyrene-maleic anhydride sulfonic acid sodium(SSMA) with different relative molecular mass was obtained by sulfonated the polystyrene-maleic anhdride.The dispersibility of 20% diflubenzuron suspension concentrate was identified by assaying and analyzing the diameter of particles,Zeta potentials and viscosities.The results showed that the optimal dispersant was SSMA,which was prepared at 75℃,and the most suitable concentration was 3%.At pH=9,the dispersion stability of suspension concentrate was the best due to the strong steric hindrance provided by completely ionizing of the molecules.Na+ or Ca2+ was able to decrease the absolute value of Zeta potential by compressing the electronic double layer thickness of particles surface,which could lead to particles aggregation due to the reduction of electric quantity and ultimately deteriorate the dispersive effect of suspension concentrate.If the ions concentration were the same,the coagulation capacity by Ca2+ was stronger than that of Na+,and the dispersion stability of suspension was worse after adding Ca2+.
2012, 29(9): 1053-1059
doi: 10.3724/SP.J.1095.2012.00490
Abstract:
The molecular interaction parameter(βm),molecular exchange energy(εm) and thermodynamic parameters(ΔGmo,ΔHmo,ΔSmo) of mixed micelle for the binary systems of polyoxyethylene(20) sorbitan ester(Tween) and oleylpolyoxyethylene(10)(Brij97) were calculated from surface tension data.The effects of the molecular structure of Tweens,the compositions of the mixed system and the temperature were discussed.For the systems investigated,it has been showed that the synergism and molar fraction of Tween(X1m) in mixed micelles increase with the increase of carbon chain of Tween.The larger the molar fraction of Tween(α1) is,the greater the free energy(ΔGmo) in Tween60/Brij97 mixed surfactants.At α1≤0.33,the mixtures show synergism at mixed micelle formation,while mixtures do not have synergism with α1>0.33;the critical micelle concentration,free energy and synergism in Tween60/Brij97 mixed micelle decrease as the temperature increase,but the enthalpy and entropy are reverse.
The molecular interaction parameter(βm),molecular exchange energy(εm) and thermodynamic parameters(ΔGmo,ΔHmo,ΔSmo) of mixed micelle for the binary systems of polyoxyethylene(20) sorbitan ester(Tween) and oleylpolyoxyethylene(10)(Brij97) were calculated from surface tension data.The effects of the molecular structure of Tweens,the compositions of the mixed system and the temperature were discussed.For the systems investigated,it has been showed that the synergism and molar fraction of Tween(X1m) in mixed micelles increase with the increase of carbon chain of Tween.The larger the molar fraction of Tween(α1) is,the greater the free energy(ΔGmo) in Tween60/Brij97 mixed surfactants.At α1≤0.33,the mixtures show synergism at mixed micelle formation,while mixtures do not have synergism with α1>0.33;the critical micelle concentration,free energy and synergism in Tween60/Brij97 mixed micelle decrease as the temperature increase,but the enthalpy and entropy are reverse.
2012, 29(9): 1060-1064
doi: 10.3724/SP.J.1095.2012.00421
Abstract:
The complex system of six kinds of different structure of alkyl aryl sulfonates(synthesized in the laboratory)/different alchol/n-decane/NaCl water microemulsions were investigated by Winsor phase diagram.The effects of molecular structure,temperature and alcohol were invetigated.The results showed that as the number of long alkyl carbon atoms in alkyl aryl sulfonate molecule increase,the values of S1,S2(the salt concentrations of middle-phase microemulsion appears or disappears),ΔS(salt concentration width) and S*(optimal concentration of salt) decrease,while the values of VM*(optimal volume of middle-phase microemulsion) and σ*(σ* means optimal solubilization) increase.Similar trends were also observed with the increase of temperature and carbon atom numbers of the alcohols and no middle phase microemulsion could be formed at 25℃.However,as the aromatic rings shift from the edge to the middle of the long carbonic chains,the values of S1,S2 and ΔS,S* decrease and those of VM* and σ* increase.
The complex system of six kinds of different structure of alkyl aryl sulfonates(synthesized in the laboratory)/different alchol/n-decane/NaCl water microemulsions were investigated by Winsor phase diagram.The effects of molecular structure,temperature and alcohol were invetigated.The results showed that as the number of long alkyl carbon atoms in alkyl aryl sulfonate molecule increase,the values of S1,S2(the salt concentrations of middle-phase microemulsion appears or disappears),ΔS(salt concentration width) and S*(optimal concentration of salt) decrease,while the values of VM*(optimal volume of middle-phase microemulsion) and σ*(σ* means optimal solubilization) increase.Similar trends were also observed with the increase of temperature and carbon atom numbers of the alcohols and no middle phase microemulsion could be formed at 25℃.However,as the aromatic rings shift from the edge to the middle of the long carbonic chains,the values of S1,S2 and ΔS,S* decrease and those of VM* and σ* increase.
2012, 29(9): 1065-1069
doi: 10.3724/SP.J.1095.2012.00465
Abstract:
The electrochemical hydrogen permeation dynamic behavior of X120 pipeline steel was investigated by Davanathan-Stachursky dual cell system.Electrochemical hydrogen charging method was used for prefabricating micro-cracks,and scanning electron microscope(SEM) was employed to observe inclusions and hydrogen induced cracking in X120 pipeline steel.The results demonstrate that the saturated anode current I∞,hydrogen flux J∞ and hydrogen effective diffusion coefficient Deff increase with the increase of charging current density.The effect of inclusions in the steel on the crack initiation depends on their chemical compositions.There are three kinds of inclusions,such as Al/Mn contained sulfide/oxide,Ti/Nb contained nitride complex and Ca-Al-O-S mixed inclusions in the experimental X120 pipeline steel.Hydrogen induced cracking is initiated easily at the sites of Al/Mn contained inclusions,the cracks nucleate and then grow along with the rolling direction.
The electrochemical hydrogen permeation dynamic behavior of X120 pipeline steel was investigated by Davanathan-Stachursky dual cell system.Electrochemical hydrogen charging method was used for prefabricating micro-cracks,and scanning electron microscope(SEM) was employed to observe inclusions and hydrogen induced cracking in X120 pipeline steel.The results demonstrate that the saturated anode current I∞,hydrogen flux J∞ and hydrogen effective diffusion coefficient Deff increase with the increase of charging current density.The effect of inclusions in the steel on the crack initiation depends on their chemical compositions.There are three kinds of inclusions,such as Al/Mn contained sulfide/oxide,Ti/Nb contained nitride complex and Ca-Al-O-S mixed inclusions in the experimental X120 pipeline steel.Hydrogen induced cracking is initiated easily at the sites of Al/Mn contained inclusions,the cracks nucleate and then grow along with the rolling direction.
2012, 29(9): 1070-1074
doi: 10.3724/SP.J.1095.2012.00416
Abstract:
A graphene modified glassy carbon electrode was fabricated for the determination of catechol.The electrochemical behaviors of the modified electrodes were investigated by cyclic voltammetry(CV).The influence of the solution pH on the modified electrode was studied by differential pulse voltammetry(DPV).It was found that there was a good linear relationship between the response current and the concentration of catechol over the range from 5.0×10-8 to 5.6×10-4 mol/L,with the correlation coefficient of 0.9919 and the detection limit of 6.68×10-9 mol/L(S/N=3).Compared with other modified electrode,the graphene modified glassy carbon electrode was convenient to prepare,and it exhibited a fast response time and long-term stability,and could be used in the determination of catechol.
A graphene modified glassy carbon electrode was fabricated for the determination of catechol.The electrochemical behaviors of the modified electrodes were investigated by cyclic voltammetry(CV).The influence of the solution pH on the modified electrode was studied by differential pulse voltammetry(DPV).It was found that there was a good linear relationship between the response current and the concentration of catechol over the range from 5.0×10-8 to 5.6×10-4 mol/L,with the correlation coefficient of 0.9919 and the detection limit of 6.68×10-9 mol/L(S/N=3).Compared with other modified electrode,the graphene modified glassy carbon electrode was convenient to prepare,and it exhibited a fast response time and long-term stability,and could be used in the determination of catechol.
2012, 29(9): 1075-1081
doi: 10.3724/SP.J.1095.2012.00478
Abstract:
On-line infrared spectroscopy was used to monitor the reaction process for synthesizing 3-amino-4-amino oxime furazan from malononitrile,sodium nitrite and hydroxylamine hydrochloride catalyzed by acetic acid.The concentration profiles and spectra of the reactant,intermediates and product were obtained by analyzing the real-time infrared spectroscopy(IR) data using chemometric methods such as multiple curve resolution-alternating least squares(MCR-ALS),heuristic evolving latent projections(HELP) and etc.A reasonable mechanism was induced by the conclusion acquired from comparing MCR-ALS with HELP.Spectral similarity between the original and the obtained spectra of the reactants and the product was close to one,which showed that the methods used in this article were accurate and reliable.The experimental results showed that the chemometric resolution combined with IR spectroscopy could effectively be applied to mechanistic study on the formation of 3-amino-4-amino oxime furazan.It would provide significant insights into the reaction mechanism.
On-line infrared spectroscopy was used to monitor the reaction process for synthesizing 3-amino-4-amino oxime furazan from malononitrile,sodium nitrite and hydroxylamine hydrochloride catalyzed by acetic acid.The concentration profiles and spectra of the reactant,intermediates and product were obtained by analyzing the real-time infrared spectroscopy(IR) data using chemometric methods such as multiple curve resolution-alternating least squares(MCR-ALS),heuristic evolving latent projections(HELP) and etc.A reasonable mechanism was induced by the conclusion acquired from comparing MCR-ALS with HELP.Spectral similarity between the original and the obtained spectra of the reactants and the product was close to one,which showed that the methods used in this article were accurate and reliable.The experimental results showed that the chemometric resolution combined with IR spectroscopy could effectively be applied to mechanistic study on the formation of 3-amino-4-amino oxime furazan.It would provide significant insights into the reaction mechanism.
2012, 29(9): 1082-1086
doi: 10.3724/SP.J.1095.2012.00458
Abstract:
A new method is proposed to determine ceftazidime using sodium nitroprusside.In an alkaline solution,a brown product is formed by the reaction of ceftazidime with sodium nitroprusside with the stoichiometric ratio of 1:2.The amount of ceftazidime can be determined owing to the absorbance of the colored product.Absorbency is linear with the concentration of ceftazidime in the range of 2.50~810 mg/L,and the regression equation is A=0.02704+0.00218ρ(mg/L) with a correlation coefficient of 0.9987.The apparent molar absorption coefficient and the detection limit are 1.2×103 L/(mol·cm) and 1.38 mg/L,respectively.This method is simple and fast,the study indicated that the method could be applied to the determination of ceftazidime in injection with satisfactory results.
A new method is proposed to determine ceftazidime using sodium nitroprusside.In an alkaline solution,a brown product is formed by the reaction of ceftazidime with sodium nitroprusside with the stoichiometric ratio of 1:2.The amount of ceftazidime can be determined owing to the absorbance of the colored product.Absorbency is linear with the concentration of ceftazidime in the range of 2.50~810 mg/L,and the regression equation is A=0.02704+0.00218ρ(mg/L) with a correlation coefficient of 0.9987.The apparent molar absorption coefficient and the detection limit are 1.2×103 L/(mol·cm) and 1.38 mg/L,respectively.This method is simple and fast,the study indicated that the method could be applied to the determination of ceftazidime in injection with satisfactory results.
2012, 29(9): 1087-1089
doi: 10.3724/SP.J.1095.2012.00451
Abstract:
(S)-3-Chloro-1-phenyl-1-propanol was synthesized asymmetrically by using catalysts(R)-α,α-diphenyl-2-pyrrolidinemethanol,(1R,2S)-2-amino-1,2-diphenylethanol and(1R,2R)-1-amino-2-indanol with amine borane complexes,with a yield of 88.3%~93.8%,ee% 81.6~87.7.These amine borane complexes are more stable and safe than the borane-tetrahydrofuran complex and borane-methyl sulfide complex.
(S)-3-Chloro-1-phenyl-1-propanol was synthesized asymmetrically by using catalysts(R)-α,α-diphenyl-2-pyrrolidinemethanol,(1R,2S)-2-amino-1,2-diphenylethanol and(1R,2R)-1-amino-2-indanol with amine borane complexes,with a yield of 88.3%~93.8%,ee% 81.6~87.7.These amine borane complexes are more stable and safe than the borane-tetrahydrofuran complex and borane-methyl sulfide complex.
2012, 29(9): 1090-1092
doi: 10.3724/SP.J.1095.2012.00464
Abstract:
A novel cyclophosphazene flame retardant monomer with allyl group,2-allyl phenoxy-pentaphenoxycyclotriphosphazene(APPCP),was synthesized by using hexachlorocyclotriphosphazene(HCCP),2-allylphenol and phenol as the starting materials.The structure of the product was characterized by FTIR,MS,1H NMR and elemental analysis.The flame retardant acrylate resin was prepared through copolymerized with APPCP and acrylate resin monomers,and the effects of APPCP on the thermal and flame-retardant properties were investigated.With the addition of 20%APPCP,the flammability class of the copolymerized acrylate resin was attained to V-0,with the limiting oxygen index(LOI) value increased to 31.2%,and the residual mass up to 23.2% at 600℃.
A novel cyclophosphazene flame retardant monomer with allyl group,2-allyl phenoxy-pentaphenoxycyclotriphosphazene(APPCP),was synthesized by using hexachlorocyclotriphosphazene(HCCP),2-allylphenol and phenol as the starting materials.The structure of the product was characterized by FTIR,MS,1H NMR and elemental analysis.The flame retardant acrylate resin was prepared through copolymerized with APPCP and acrylate resin monomers,and the effects of APPCP on the thermal and flame-retardant properties were investigated.With the addition of 20%APPCP,the flammability class of the copolymerized acrylate resin was attained to V-0,with the limiting oxygen index(LOI) value increased to 31.2%,and the residual mass up to 23.2% at 600℃.
2012, 29(9): 1093-1095
doi: 10.3724/SP.J.1095.2012.00338
Abstract:
Four double-ring difluorometheneoxy-bridged benzene compounds were synthesized and characterized by means of IR,1H NMR,13C NMR,19F NMR and MS.Their viscosities at different temperatures were also measured and analyzed by using liquid dynamic rheometer.It was found that these compounds not only have super low viscosity and small temperature-dependent viscosity,but also can be used as the solvent of LC to replace ester components.They may be used as the LC solvent to improve the low-temperature response speed of LCD.
Four double-ring difluorometheneoxy-bridged benzene compounds were synthesized and characterized by means of IR,1H NMR,13C NMR,19F NMR and MS.Their viscosities at different temperatures were also measured and analyzed by using liquid dynamic rheometer.It was found that these compounds not only have super low viscosity and small temperature-dependent viscosity,but also can be used as the solvent of LC to replace ester components.They may be used as the LC solvent to improve the low-temperature response speed of LCD.
2012, 29(9): 1096-1098
doi: 10.3724/SP.J.1095.2012.00469
Abstract:
Under the protection of pure N2,La-doped Bi2Te3 and Bi0.5Sb1.5Te3 were prepared by the method of electromagnetic induction.The structures and morphologies of the samples were characterized using X-ray diffraction,inductively coupled plasma and scanning electron microscopy.The electricity conductivity(σ),Seebeck coefficient(S) and thermal conductivity(κ) were studied.The results showed that La-doped samples have lower thermal conductivity and enhanced figure of merit(ZT).The thermoelectric figure of merit of La-doped Bi0.5Sb1.5Te3 were improved up to 1 at room temperature.
Under the protection of pure N2,La-doped Bi2Te3 and Bi0.5Sb1.5Te3 were prepared by the method of electromagnetic induction.The structures and morphologies of the samples were characterized using X-ray diffraction,inductively coupled plasma and scanning electron microscopy.The electricity conductivity(σ),Seebeck coefficient(S) and thermal conductivity(κ) were studied.The results showed that La-doped samples have lower thermal conductivity and enhanced figure of merit(ZT).The thermoelectric figure of merit of La-doped Bi0.5Sb1.5Te3 were improved up to 1 at room temperature.
