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2011 Volume 28 Issue 4
2011, 28(4): 367-375
doi: 10.3724/SP.J.1095.2011.00364
Abstract:
With increasing applications of immune assay,the synthesis of artificial antigen with good stability and immunogenic is the key and premise to prepare the antibody and to establish the method for small molecule immune assay.The progress of synthesis and design method of hapten,carrier selection and the couple method of hapten with carrier are reviewed in this paper.In addition,some questions of the synthesis of small molecule artificial antigen were also discussed.
With increasing applications of immune assay,the synthesis of artificial antigen with good stability and immunogenic is the key and premise to prepare the antibody and to establish the method for small molecule immune assay.The progress of synthesis and design method of hapten,carrier selection and the couple method of hapten with carrier are reviewed in this paper.In addition,some questions of the synthesis of small molecule artificial antigen were also discussed.
2011, 28(4): 376-381
doi: 10.3724/SP.J.1095.2011.00381
Abstract:
2-Amino-3,5-dinitropyridine(1) and 2-amino-3,5-dinitropyridine-1-oxide(3) have been aminated by various nucleophilic substitution reaction,using hydroxylamine hydrochloride,4-amino-1,2,4-triazole and 1,1,1-trimethylhydrazinium iodide as aminating agents.Based on amination via vicarious nucleophilic substitution(VNS) of hydrogen,the stereo-electronic effects of aminating agents and reactants on the composition and yield of target compounds were discussed.Reactants 1 and 3 were aminated at the 6-position and 4-position using hydroxylamine with a yield in the range of 64%~89%.Reactions of 1 and 3 respectively with 4-amino-1,2,4-triazole or 1,1,1-trimethylhydrazinium generated compounds which were aminated at the 6-position,with a yield over 90%.Under the same conditions,the yields for the target compounds were improved with the increase of the activities of aminating agents.
2-Amino-3,5-dinitropyridine(1) and 2-amino-3,5-dinitropyridine-1-oxide(3) have been aminated by various nucleophilic substitution reaction,using hydroxylamine hydrochloride,4-amino-1,2,4-triazole and 1,1,1-trimethylhydrazinium iodide as aminating agents.Based on amination via vicarious nucleophilic substitution(VNS) of hydrogen,the stereo-electronic effects of aminating agents and reactants on the composition and yield of target compounds were discussed.Reactants 1 and 3 were aminated at the 6-position and 4-position using hydroxylamine with a yield in the range of 64%~89%.Reactions of 1 and 3 respectively with 4-amino-1,2,4-triazole or 1,1,1-trimethylhydrazinium generated compounds which were aminated at the 6-position,with a yield over 90%.Under the same conditions,the yields for the target compounds were improved with the increase of the activities of aminating agents.
2011, 28(4): 382-386
doi: 10.3724/SP.J.1095.2011.00372
Abstract:
N,N-Dimethylformamide-dimethyl acetal(DMF-DMA) was refluxed with the corresponding aromatic or heterocyclic compounds to prepare the intermediates 3-(dimethylamino)-1-(substituted) prop-2-en-1-one with a yield of 71.2%~85.2%.By refluxing the obtained intermediates with guanidine hydrochloride in ethanol and in the presence of sodium ethoxide,fourteen 4-substituted-2-amino-pyrimidines were obtained in good yield of 66.6%~86.1%.All the products were confirmed by NMR,mass spectrometry,and elemental analysis.
N,N-Dimethylformamide-dimethyl acetal(DMF-DMA) was refluxed with the corresponding aromatic or heterocyclic compounds to prepare the intermediates 3-(dimethylamino)-1-(substituted) prop-2-en-1-one with a yield of 71.2%~85.2%.By refluxing the obtained intermediates with guanidine hydrochloride in ethanol and in the presence of sodium ethoxide,fourteen 4-substituted-2-amino-pyrimidines were obtained in good yield of 66.6%~86.1%.All the products were confirmed by NMR,mass spectrometry,and elemental analysis.
2011, 28(4): 387-393
doi: 10.3724/SP.J.1095.2011.00347
Abstract:
A series of ionic organotin(Ⅳ) complexes with general formula [HNR3][(PhCH2)3Sn(μ2-SCH2COO)Cl]、[HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH and [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] were synthesized by the reaction of organic acid with organotin halide in the presence of an organic base.The results of the anti-tumor,bactericidal and acaricidal activity show that some complexes have good biological activity.The inhibition rate of [HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH and [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for A-549,HCT-8 and Bel-7402 was about 90%,the mortality rate of [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for Gibberella zeae,Alternaria solani,Phomopsis asparagi,Physalospora piricola,Cercospora arachidicol was 100%,the mortality rate of [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for acaricidal activity was more than 90%.
A series of ionic organotin(Ⅳ) complexes with general formula [HNR3][(PhCH2)3Sn(μ2-SCH2COO)Cl]、[HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH and [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] were synthesized by the reaction of organic acid with organotin halide in the presence of an organic base.The results of the anti-tumor,bactericidal and acaricidal activity show that some complexes have good biological activity.The inhibition rate of [HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH and [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for A-549,HCT-8 and Bel-7402 was about 90%,the mortality rate of [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for Gibberella zeae,Alternaria solani,Phomopsis asparagi,Physalospora piricola,Cercospora arachidicol was 100%,the mortality rate of [HNR3][MeCy2ClSnO2CCH2-CO2SnClCy2Me] complexes for acaricidal activity was more than 90%.
2011, 28(4): 394-401
doi: 10.3724/SP.J.1095.2011.00369
Abstract:
Two new complexes [Nd(oba)(Hoba)(H2O)2]·H2O(1) and Sm(oba)(Hoba)(phen)(2)(H2oba=4,4'-oxybis(benzoic acid),phen=1,10-phenanthroline) were prepared by hydrothermal method.The X-ray diffraction analysis indicated that the two complexes crystallized in monoclinic system with space group C2/c.The cell parameter of complex 1 are:a=2.736 80(5) nm,b=0.956 35(2) nm,c=2.170 93(4) nm,β=97.685 0(10)°,V=5.631 02(19) nm3,Z=8,F(000)=2 854,R(int)=0.022 6.In complex 1,oba and Hoba ligands connect the neighboring Nd3+ ions to form a 2D network with novel topology of{42·6}{43·6·84·102}{4}.Each Nd3+ ion is eight-coordinated by six oxygen atoms from oba and Hoba ligands and two O atoms from waters.3D structure is achieved through O——H…O hydrogen bondings between the coordinated water molecules and Hoba and between Hoba ligands.The cell parameters of complex 2 are:a=1.352 60(5) nm,b=1.936 86(6) nm,c=2.728 59(8) nm,β=99.867(2)°,V=7.042 6(4) nm3,Z=8,F(000)=3 368,R(int)=0.039 4.In complex 2,the coordination modes of oba and Hoba are similar to those in complex 1.Sm3+ ion is eight-coordinated by six O atoms from oba and Hoba ligands and two N atoms from phen.The two neighboring Sm3+ ions are connected by COO- groups and form dimeric units,which are further joined by oba lignds to assemble into a 1D chain-like complex.The 2D network of complex 2 is formed through the hydrogen bondings between the uncoordinated carboxyl of the Hoba ligands.Moreover,3D superamolecular structure of complex 2 is formed through the π-π stacking interactions between phen molecules.The UV Vis spectrum of complex 1 shows characteristic transitions of Nd3+ with 4I9/2→4G7/2+4G9/2+2K13/2 and 4I9/2→4G5/2+4G7/2 at 510~538 nm and 566~600 nm,respectively;the fluorescence spectrum of complex 2 shows characteristic emission of Sm3+ with the transitions of 4G5/2→6H5/2,4G5/2→6H7/2 and 4G5/2→6H9/2.
Two new complexes [Nd(oba)(Hoba)(H2O)2]·H2O(1) and Sm(oba)(Hoba)(phen)(2)(H2oba=4,4'-oxybis(benzoic acid),phen=1,10-phenanthroline) were prepared by hydrothermal method.The X-ray diffraction analysis indicated that the two complexes crystallized in monoclinic system with space group C2/c.The cell parameter of complex 1 are:a=2.736 80(5) nm,b=0.956 35(2) nm,c=2.170 93(4) nm,β=97.685 0(10)°,V=5.631 02(19) nm3,Z=8,F(000)=2 854,R(int)=0.022 6.In complex 1,oba and Hoba ligands connect the neighboring Nd3+ ions to form a 2D network with novel topology of{42·6}{43·6·84·102}{4}.Each Nd3+ ion is eight-coordinated by six oxygen atoms from oba and Hoba ligands and two O atoms from waters.3D structure is achieved through O——H…O hydrogen bondings between the coordinated water molecules and Hoba and between Hoba ligands.The cell parameters of complex 2 are:a=1.352 60(5) nm,b=1.936 86(6) nm,c=2.728 59(8) nm,β=99.867(2)°,V=7.042 6(4) nm3,Z=8,F(000)=3 368,R(int)=0.039 4.In complex 2,the coordination modes of oba and Hoba are similar to those in complex 1.Sm3+ ion is eight-coordinated by six O atoms from oba and Hoba ligands and two N atoms from phen.The two neighboring Sm3+ ions are connected by COO- groups and form dimeric units,which are further joined by oba lignds to assemble into a 1D chain-like complex.The 2D network of complex 2 is formed through the hydrogen bondings between the uncoordinated carboxyl of the Hoba ligands.Moreover,3D superamolecular structure of complex 2 is formed through the π-π stacking interactions between phen molecules.The UV Vis spectrum of complex 1 shows characteristic transitions of Nd3+ with 4I9/2→4G7/2+4G9/2+2K13/2 and 4I9/2→4G5/2+4G7/2 at 510~538 nm and 566~600 nm,respectively;the fluorescence spectrum of complex 2 shows characteristic emission of Sm3+ with the transitions of 4G5/2→6H5/2,4G5/2→6H7/2 and 4G5/2→6H9/2.
2011, 28(4): 402-407
doi: 10.3724/SP.J.1095.2011.00353
Abstract:
ZnO microrod films has been prepared by simple low temperature hydrothermal approach.The films treated with octyltrimethoxysilane and dodecafluoroheptyl-propyl-trimethoxylsilane show super-hydrophobic properties.The static contact angles for water are (150±1.3)° and (155±1.5)°,and the slide angles are about 5° and 3°,respectively.It is believed that the super-hydrophobic property of the modified ZnO microrod films is mainly caused by the microstructures of the films and the modification of octyltrimethoxysilane or dodecafluoroheptyl-propyl-trimethoxylsilane with low surface energy on surfaces.The wettability of the ZnO submicrorod films is also discussed on the basis of Cassie theory.
ZnO microrod films has been prepared by simple low temperature hydrothermal approach.The films treated with octyltrimethoxysilane and dodecafluoroheptyl-propyl-trimethoxylsilane show super-hydrophobic properties.The static contact angles for water are (150±1.3)° and (155±1.5)°,and the slide angles are about 5° and 3°,respectively.It is believed that the super-hydrophobic property of the modified ZnO microrod films is mainly caused by the microstructures of the films and the modification of octyltrimethoxysilane or dodecafluoroheptyl-propyl-trimethoxylsilane with low surface energy on surfaces.The wettability of the ZnO submicrorod films is also discussed on the basis of Cassie theory.
2011, 28(4): 408-413
doi: 10.3724/SP.J.1095.2011.00356
Abstract:
Waterborne polyurethane(WPU) emulsion modified by antimony doped tin oxide(ATO) nanoparticles(APU) was prepared with isophorone-diisocyanate(IPDI),polyether diol(N-210),dimethylol propionic acid(DMPA),diethyleneglycol(DEG),trimethylolpropane(TMP) and ATO nanoparticles.Particle size testing and electron transmission microscopy observation showed that ATO nanoparticles was dispersed well in WPU and emulsion particle size was less than 100 nm.FTIR analysis suggested that chemical interaction existed between ATO nanoparticles and WPU.It is found from thermogravimetric analysis(TGA) that the addition of ATO nanoparticles had improved the thermal stability of WPU with the maximum 20℃ increase of the maximum thermal decomposition temperature.UV-visible-near infrared absorption and thermal insulation performance tests showed that the film's transmittance at 800~2500 nm gradually decreased with the increase of the ATO addition amount,while the coating transmittance in the visible region was still more than 70%.Moreover,the thermal resistance rate increased from 1.34×10-2 m2·℃/W to 3.17×10-2 m2·℃/W.
Waterborne polyurethane(WPU) emulsion modified by antimony doped tin oxide(ATO) nanoparticles(APU) was prepared with isophorone-diisocyanate(IPDI),polyether diol(N-210),dimethylol propionic acid(DMPA),diethyleneglycol(DEG),trimethylolpropane(TMP) and ATO nanoparticles.Particle size testing and electron transmission microscopy observation showed that ATO nanoparticles was dispersed well in WPU and emulsion particle size was less than 100 nm.FTIR analysis suggested that chemical interaction existed between ATO nanoparticles and WPU.It is found from thermogravimetric analysis(TGA) that the addition of ATO nanoparticles had improved the thermal stability of WPU with the maximum 20℃ increase of the maximum thermal decomposition temperature.UV-visible-near infrared absorption and thermal insulation performance tests showed that the film's transmittance at 800~2500 nm gradually decreased with the increase of the ATO addition amount,while the coating transmittance in the visible region was still more than 70%.Moreover,the thermal resistance rate increased from 1.34×10-2 m2·℃/W to 3.17×10-2 m2·℃/W.
2011, 28(4): 414-420
doi: 10.3724/SP.J.1095.2011.00337
Abstract:
A novel MnO2/MSAC(micro-spherical activated carbon base on mesocarbon microbead) composite,which might be used as an electrode material in electrochemical capacitor,was prepared by dispersing thermally decomposed MnO2 from manganese nitrates on MSAC.The morphology and crystal structure of the composite were investigated by scanning electron microscopy(SEM),transmission electron microscope(TEM) and X-ray diffraction(XRD),respectively.The electrochemical properties of the electrode were studied by cyclic voltammetry(CV),galvanostatic charge-discharge,and electrochemical impedance spectroscopy(EIS) in 1.0 mol/L LiPF6.Our results showed that the MnO2 particles dispersed on MSAC have particle size in the range of 100~160 nm,the initial specific capacitance of the MSAC/MnO2 and single MSAC electrode are 186 F/g and 167 F/g respectively at 2×10-3 A/cm2 current density.The Coulombic efficiency of MnO2/MSAC spherical compound materials capacitor remained above 95% after 200 charge and discharge cycles.In addition,the charge-discharge curve of the MSAC/MnO2 electrode showed typical capacitive behavior with a good linearity,and the CV curve also showed good rectangular features,high energy density and good power performance.
A novel MnO2/MSAC(micro-spherical activated carbon base on mesocarbon microbead) composite,which might be used as an electrode material in electrochemical capacitor,was prepared by dispersing thermally decomposed MnO2 from manganese nitrates on MSAC.The morphology and crystal structure of the composite were investigated by scanning electron microscopy(SEM),transmission electron microscope(TEM) and X-ray diffraction(XRD),respectively.The electrochemical properties of the electrode were studied by cyclic voltammetry(CV),galvanostatic charge-discharge,and electrochemical impedance spectroscopy(EIS) in 1.0 mol/L LiPF6.Our results showed that the MnO2 particles dispersed on MSAC have particle size in the range of 100~160 nm,the initial specific capacitance of the MSAC/MnO2 and single MSAC electrode are 186 F/g and 167 F/g respectively at 2×10-3 A/cm2 current density.The Coulombic efficiency of MnO2/MSAC spherical compound materials capacitor remained above 95% after 200 charge and discharge cycles.In addition,the charge-discharge curve of the MSAC/MnO2 electrode showed typical capacitive behavior with a good linearity,and the CV curve also showed good rectangular features,high energy density and good power performance.
2011, 28(4): 421-425
doi: 10.3724/SP.J.1095.2011.00358
Abstract:
The inclusions of lornoxicam(LX) by β-cyclodextrin(β-CD),hydroxypropyl-β-cyclodextrin(HP-β-CD),and sulfobutyl ether-β-cyclodextrin(SBE-β-CD) were studied by fluorescence spectroscopy,differential scanning calorimetry(DSC) and NMR at different pH and temperature.The results showed that the 1:1 inclusion compounds were formed between lornoxicam and CDs.Based on the formation constants,the interactions between lornoxicam and the three CDs follow an order of SBE-β-CD >HP-β-CD >β-CD.
The inclusions of lornoxicam(LX) by β-cyclodextrin(β-CD),hydroxypropyl-β-cyclodextrin(HP-β-CD),and sulfobutyl ether-β-cyclodextrin(SBE-β-CD) were studied by fluorescence spectroscopy,differential scanning calorimetry(DSC) and NMR at different pH and temperature.The results showed that the 1:1 inclusion compounds were formed between lornoxicam and CDs.Based on the formation constants,the interactions between lornoxicam and the three CDs follow an order of SBE-β-CD >HP-β-CD >β-CD.
2011, 28(4): 426-431
doi: 10.3724/SP.J.1095.2011.00237
Abstract:
Cetyl trimethyl ammonium bromide/sorbitan monostearate(Span-60) microemulsion-based gel(CTAB/Span-60 MBG) having good stability in aqueous solution was successfully prepared.The mass percentage of Span-60 in emulsifier mixture(EM,the mixture of n-butanol and Span-60) was determined.The catalytic activity and stereoselectivity of lipase immobilized in CTAB/Span-60 MBG were tested using the esterification of hexanoic acid and hexanol,the hydrolysis of α-glyceryl monostearate and the stereoselective esterification of racemic ibuprofen and octanol as probes,respectively.The results showed that CTAB/Span-60 MBG with good mechanical strength could be achieved when the mass percentage of Span-60 in EM was less than 57%.In organic solvent,the catalytic esterification activity of lipase in this MBG increased gradually with the increase of the content of Span-60 in EM at the first stage and reached maximum at 35% and then decreased slightly with further increase of the content,and was higher than that in CTAB MBG,within the investigated content of Span-60.This immobilized lipase could catalyze the hydrolysis of α-glyceryl monostearate in aqueous solution and the reaction conversion rate didn't change any more after 24 h.The catalytic hydrolytic activity decreased by 13.68% after 9 re-usage times.This suggests that lipase in CTAB/Span-60 MBG could be separated and reused.Lipase in this MBG also selectively catalyzed S-enantiomer ibuprofen to S-enantiomer ester and the excessive enantiomeric product(eee) of the latter gradually decreased with the proceeding of the reaction,but showing better stereoselectivity than CTAB MBG.As a promising carrier for immobilizing lipase,CTAB/Span-60 MBG could be used in biosynthesis and biotransformation not only in organic solvent but also in aqueous solution.
Cetyl trimethyl ammonium bromide/sorbitan monostearate(Span-60) microemulsion-based gel(CTAB/Span-60 MBG) having good stability in aqueous solution was successfully prepared.The mass percentage of Span-60 in emulsifier mixture(EM,the mixture of n-butanol and Span-60) was determined.The catalytic activity and stereoselectivity of lipase immobilized in CTAB/Span-60 MBG were tested using the esterification of hexanoic acid and hexanol,the hydrolysis of α-glyceryl monostearate and the stereoselective esterification of racemic ibuprofen and octanol as probes,respectively.The results showed that CTAB/Span-60 MBG with good mechanical strength could be achieved when the mass percentage of Span-60 in EM was less than 57%.In organic solvent,the catalytic esterification activity of lipase in this MBG increased gradually with the increase of the content of Span-60 in EM at the first stage and reached maximum at 35% and then decreased slightly with further increase of the content,and was higher than that in CTAB MBG,within the investigated content of Span-60.This immobilized lipase could catalyze the hydrolysis of α-glyceryl monostearate in aqueous solution and the reaction conversion rate didn't change any more after 24 h.The catalytic hydrolytic activity decreased by 13.68% after 9 re-usage times.This suggests that lipase in CTAB/Span-60 MBG could be separated and reused.Lipase in this MBG also selectively catalyzed S-enantiomer ibuprofen to S-enantiomer ester and the excessive enantiomeric product(eee) of the latter gradually decreased with the proceeding of the reaction,but showing better stereoselectivity than CTAB MBG.As a promising carrier for immobilizing lipase,CTAB/Span-60 MBG could be used in biosynthesis and biotransformation not only in organic solvent but also in aqueous solution.
2011, 28(4): 432-437
doi: 10.3724/SP.J.1095.2011.00379
Abstract:
Surface desorption atmospheric pressure chemical ionization tandem mass spectrometry(SDAPCIMSn),a novel method,was developed for the direct detection of sinapine in radish taproot samples,which allowed quantitative in situ studies of the decline of sinapine in radish taproot samples under different circumstances.The data demonstrated that at room temperature(25℃),sinapine in radish taproot declined gradually over a short time to a certain level,then the decline speed became slow.It was also found that sinapine declined very slowly at low temperature conditions(≤ 4℃),suggesting that the fresh radish taproot should be stored at low temperature to maintain the maximal amount of sinapine.When the radish juice was exposed to the air,the sinapine decline rate was more than 300 times higher than that of daily stored radish.All the decline processes were fitted with a first order linear equation.
Surface desorption atmospheric pressure chemical ionization tandem mass spectrometry(SDAPCIMSn),a novel method,was developed for the direct detection of sinapine in radish taproot samples,which allowed quantitative in situ studies of the decline of sinapine in radish taproot samples under different circumstances.The data demonstrated that at room temperature(25℃),sinapine in radish taproot declined gradually over a short time to a certain level,then the decline speed became slow.It was also found that sinapine declined very slowly at low temperature conditions(≤ 4℃),suggesting that the fresh radish taproot should be stored at low temperature to maintain the maximal amount of sinapine.When the radish juice was exposed to the air,the sinapine decline rate was more than 300 times higher than that of daily stored radish.All the decline processes were fitted with a first order linear equation.
2011, 28(4): 438-442
doi: 10.3724/SP.J.1095.2011.00343
Abstract:
The enthalpies of dissolution of paclitaxel in dimethylsulfoxide(DMSO) was reported.The differential enthalpy(ΔdifHm) and the molar enthalpy(ΔsolHm) were determined,and the relationship between the amount of heat released and the amount of solute was also established.The corresponding kinetic equation that describes the dissolution process is (da)/(dt)=2.92×10-4×(1-a)1.00,and the kinetic parameters are obtained as follows:t1/2=50.43 min,ΔsolHm=32.67 kJ/mol,and ΔsolSm=-204.93 J/(mol·K).The result not only provides a simple method for the determination of the half-life for drugs,but it can also offer a theoretical reference for the clinical application of paclitaxel using microcalorimeter.
The enthalpies of dissolution of paclitaxel in dimethylsulfoxide(DMSO) was reported.The differential enthalpy(ΔdifHm) and the molar enthalpy(ΔsolHm) were determined,and the relationship between the amount of heat released and the amount of solute was also established.The corresponding kinetic equation that describes the dissolution process is (da)/(dt)=2.92×10-4×(1-a)1.00,and the kinetic parameters are obtained as follows:t1/2=50.43 min,ΔsolHm=32.67 kJ/mol,and ΔsolSm=-204.93 J/(mol·K).The result not only provides a simple method for the determination of the half-life for drugs,but it can also offer a theoretical reference for the clinical application of paclitaxel using microcalorimeter.
2011, 28(4): 443-447
doi: 10.3724/SP.J.1095.2011.00255
Abstract:
Eight standard polyacrylic acid(PAA) samples with different molecular mass were obtained via an isothermal precipitation grading method by using dioxane as solvent and petroleum ether as precipitator.Their peak molecular mass and molecular mass distributions were determined from an asymptotic calibration method.The results showed that the average relative errors for Mη are about 7% and 9% compared with those obtained using viscometry end-group titration,respectively.When these standard samples were used for determining the molecular mass as well as their distributions for actual PAA samples,the average relative error is less than 10%,which is superior to that using polyethylene glycol(PEG) as standard samples(about 30%).The PAA standard samples in gel permeation chromatography(GPC) might be extended to other anionic polyelectrolytes with similar structure for the same purpose.
Eight standard polyacrylic acid(PAA) samples with different molecular mass were obtained via an isothermal precipitation grading method by using dioxane as solvent and petroleum ether as precipitator.Their peak molecular mass and molecular mass distributions were determined from an asymptotic calibration method.The results showed that the average relative errors for Mη are about 7% and 9% compared with those obtained using viscometry end-group titration,respectively.When these standard samples were used for determining the molecular mass as well as their distributions for actual PAA samples,the average relative error is less than 10%,which is superior to that using polyethylene glycol(PEG) as standard samples(about 30%).The PAA standard samples in gel permeation chromatography(GPC) might be extended to other anionic polyelectrolytes with similar structure for the same purpose.
2011, 28(4): 448-453
doi: 10.3724/SP.J.1095.2011.00395
Abstract:
A preconcentration column packed with home-made sulfonated glycidyl methacrylate(GMA)-grafted-polytetrafluoroethylene(PTFE) polymer(PTFE-g-GMA-SO3H) fiber,coupled with high-performance liquid chromatography(HPLC) and flow injection,fiber was developed for trace melamine determination in the samples.The on-line determination method using the fiber as adsorbent for trace melamine in two milk sample was demonstrated.The conditions for preconcentration and elution of melamine were optimized.In addition,analytical performance of trace melamine determination was acquired in this article.The enrichment factor for melamine was 300 and the detection limits was 1.13×10-2 mg/L.The relative standard derivation was 7.6%(n=9) when the melamine concentration was 0.2 mg/L,and the recovery of samples was 98% and 102.5%,respectively.
A preconcentration column packed with home-made sulfonated glycidyl methacrylate(GMA)-grafted-polytetrafluoroethylene(PTFE) polymer(PTFE-g-GMA-SO3H) fiber,coupled with high-performance liquid chromatography(HPLC) and flow injection,fiber was developed for trace melamine determination in the samples.The on-line determination method using the fiber as adsorbent for trace melamine in two milk sample was demonstrated.The conditions for preconcentration and elution of melamine were optimized.In addition,analytical performance of trace melamine determination was acquired in this article.The enrichment factor for melamine was 300 and the detection limits was 1.13×10-2 mg/L.The relative standard derivation was 7.6%(n=9) when the melamine concentration was 0.2 mg/L,and the recovery of samples was 98% and 102.5%,respectively.
2011, 28(4): 454-457
doi: 10.3724/SP.J.1095.2011.00087
Abstract:
Tea polysaccharide conjugates(TPC) named TPC-1 were prepared from low-grade green tea by extraction through complex enzymes method and purified by diethylaminoethyl(DEAE) cellulose(DE-52) column chromatography,while TPC-2 was prepared by extraction with boiling water and purified by Sephadex G-200 column chromatography.TPC-1 and TPC-2 were incubated respectively at 98℃ for 5.0 h.A single symmetrical peak corresponding to the main homogeneous component,TPC-1a in the chromatogram of high performance gel permeation chromatography(HPGPC) was split into two adjacent peaks representing two different components of TPC-1a-1 and TPC-1a-2.Circular dichroism(CD) spectra showed an additional positive Cotton effect for the peak at 216 nm along with the peak at 194 nm.HPGPC showed that incubation in water at 98℃ for 5.0 h has no effects on TPC-2 that contained two homogeneous components of TPC-2a and TPC-2b.The CD spectra of the treated sample revealed that the positive Cotton effects for peaks at 203 and 215 nm disappeared,while it retained for the one at 272 nm.The solution conformation and homogeneous component distribution of TPC-1 had been changed by heat treatment.But only solution conformation had been changed for TPC-2.
Tea polysaccharide conjugates(TPC) named TPC-1 were prepared from low-grade green tea by extraction through complex enzymes method and purified by diethylaminoethyl(DEAE) cellulose(DE-52) column chromatography,while TPC-2 was prepared by extraction with boiling water and purified by Sephadex G-200 column chromatography.TPC-1 and TPC-2 were incubated respectively at 98℃ for 5.0 h.A single symmetrical peak corresponding to the main homogeneous component,TPC-1a in the chromatogram of high performance gel permeation chromatography(HPGPC) was split into two adjacent peaks representing two different components of TPC-1a-1 and TPC-1a-2.Circular dichroism(CD) spectra showed an additional positive Cotton effect for the peak at 216 nm along with the peak at 194 nm.HPGPC showed that incubation in water at 98℃ for 5.0 h has no effects on TPC-2 that contained two homogeneous components of TPC-2a and TPC-2b.The CD spectra of the treated sample revealed that the positive Cotton effects for peaks at 203 and 215 nm disappeared,while it retained for the one at 272 nm.The solution conformation and homogeneous component distribution of TPC-1 had been changed by heat treatment.But only solution conformation had been changed for TPC-2.
2011, 28(4): 458-463
doi: 10.3724/SP.J.1095.2011.00326
Abstract:
The interactions of organic pesticide pollutants including,dichlorvos(DDVP),omethoate(OME),dimethoate(DIM) and plenazine-1-carboxylic acid(PCA),with the telomere DNA were investigated with ultraviolet spectroscopy,fluorescence spectroscopy and circular dichroism(CD).The results indicated that the organic pesticide pollutants interact with DNA mainly through the intercalative mode.The apparent binding constants of organic pesticides with DNA were calculated to be 1.17×106,1.48×106,4.52×105,and 1.80×106 L/mol,respectively.The apparent binding constants revealed that the order of the relative binding affinity is PCA >DIM >DDVP >OME.The CD measurement indicated that these organic pesticide pollutants caused instability of the structure of the duplex DNA by weakening the π-π stacking of DNA base pairs.To some extent,it also affected the secondary structure of DNA,leading to the relaxing of the twin helix structure.
The interactions of organic pesticide pollutants including,dichlorvos(DDVP),omethoate(OME),dimethoate(DIM) and plenazine-1-carboxylic acid(PCA),with the telomere DNA were investigated with ultraviolet spectroscopy,fluorescence spectroscopy and circular dichroism(CD).The results indicated that the organic pesticide pollutants interact with DNA mainly through the intercalative mode.The apparent binding constants of organic pesticides with DNA were calculated to be 1.17×106,1.48×106,4.52×105,and 1.80×106 L/mol,respectively.The apparent binding constants revealed that the order of the relative binding affinity is PCA >DIM >DDVP >OME.The CD measurement indicated that these organic pesticide pollutants caused instability of the structure of the duplex DNA by weakening the π-π stacking of DNA base pairs.To some extent,it also affected the secondary structure of DNA,leading to the relaxing of the twin helix structure.
2011, 28(4): 464-470
doi: 10.3724/SP.J.1095.2011.00340
Abstract:
Two pyridyl imidazo [4,5-f]1,10-phenanthroline derivates,namely 2-(3-pyridyl)-imidazo[4,5-f] 1,10-phenanthroline(G1) and 2-(4-pyridyl) imidazo [4,5-f]1,10-phenanthroline(G2),were synthesized and characterized by elemental analysis,1H NMR and MS.Under various concentrations of cucurbit [n] urils(Q[n],n=6,7),the interaction of Q[n] with G1 and G2 were studied in buffer solutions with different pH values by using UV-Vis spectroscopy and fluorescence spectrophotometry.The results revealed that cucurbit [n] urils(n=6,7) form a 1:1 complex with G1,and Q[6] form a 1:1 complex with G2 in acidic solution,fluorescent sensitizing effects of both Q[6] and Q[7] toward guests were determined.Under acidic solution Q[7] formed a 2:1 complex with G2,and a fluorescent quenching effect of Q[7] on G2 was observed.Association constants(K) of Q[n](n=6,7) with G1 were found to be 3.00×104 L/mol,1.86×104 L/mol respectively,while those of Q[n](n=6,7) with G2 are 1.64×104 L/mol and 1.01×103 L/mol respectively.With decreasing acidity of the systems,the interaction between guests and Q[n](n=6,7) weakened and no interaction was observed under neutral conditions.
Two pyridyl imidazo [4,5-f]1,10-phenanthroline derivates,namely 2-(3-pyridyl)-imidazo[4,5-f] 1,10-phenanthroline(G1) and 2-(4-pyridyl) imidazo [4,5-f]1,10-phenanthroline(G2),were synthesized and characterized by elemental analysis,1H NMR and MS.Under various concentrations of cucurbit [n] urils(Q[n],n=6,7),the interaction of Q[n] with G1 and G2 were studied in buffer solutions with different pH values by using UV-Vis spectroscopy and fluorescence spectrophotometry.The results revealed that cucurbit [n] urils(n=6,7) form a 1:1 complex with G1,and Q[6] form a 1:1 complex with G2 in acidic solution,fluorescent sensitizing effects of both Q[6] and Q[7] toward guests were determined.Under acidic solution Q[7] formed a 2:1 complex with G2,and a fluorescent quenching effect of Q[7] on G2 was observed.Association constants(K) of Q[n](n=6,7) with G1 were found to be 3.00×104 L/mol,1.86×104 L/mol respectively,while those of Q[n](n=6,7) with G2 are 1.64×104 L/mol and 1.01×103 L/mol respectively.With decreasing acidity of the systems,the interaction between guests and Q[n](n=6,7) weakened and no interaction was observed under neutral conditions.
2011, 28(4): 471-477
doi: 10.3724/SP.J.1095.2011.00376
Abstract:
Gas chromatography-mass spectrometry(GC-MS) was employed for the determination of organic pollutants in recirculating water of a paper-recycling industry.Origins of the detected organics and potential pollutions on the environment and human being were discussed.Their contents in water at different production stages were compared.Water samples were first pre-treated by liquid-liquid extraction using methyl tertbutylether(MTBE) with the presence of heptadecanoic acid(C17) as the internal standard.They were then treated by bis(trimethylsilyl) trifluoroacetamide(BSTFA) and trimethylchlorosilane(TMCS) in pyridine,followed by GC-MS analysis for the detection of respective trimethylsilyl esters formed at different stages.Using this approach,nearly 50 kinds of organic chemicals,such as resin acids,fatty acids,additives and their ramifications were detected in the processed water.And the resin acids were mainly existed in pulping water,which may come from secondary fibers and sizing agents.The fatty acids,aromatic acids and their derivatives,which may come from secondary fibers,impurities and additives,such as printing ink,plastic matters,surface active agents,were mainly existed in the white water and mixed water coming out of the mill.It was found that the mixed water contained most kinds of organic chemicals while the vacuum pumping water contained the least organic chemicals.The main chemicals contained in vacuum water were aromatic acids.There are large mounts of fatty acids,aromatic acids and theirs derivations in the wastewater of each papermaking processes,most of them are brought by the adding of secondary fiber and other additives.These organics are harmful to the environment,and difficult to be eliminated by sedimentation and flocculation.Therefore,in order to reduce the pollution of the organic pollutants in effluent wastewater,it is necessary to avoid adding phthalic acid and ester of phthalic acid.The addition of additives of long chain fatty acids and aromatic compound should be minimized in the papermaking processes.
Gas chromatography-mass spectrometry(GC-MS) was employed for the determination of organic pollutants in recirculating water of a paper-recycling industry.Origins of the detected organics and potential pollutions on the environment and human being were discussed.Their contents in water at different production stages were compared.Water samples were first pre-treated by liquid-liquid extraction using methyl tertbutylether(MTBE) with the presence of heptadecanoic acid(C17) as the internal standard.They were then treated by bis(trimethylsilyl) trifluoroacetamide(BSTFA) and trimethylchlorosilane(TMCS) in pyridine,followed by GC-MS analysis for the detection of respective trimethylsilyl esters formed at different stages.Using this approach,nearly 50 kinds of organic chemicals,such as resin acids,fatty acids,additives and their ramifications were detected in the processed water.And the resin acids were mainly existed in pulping water,which may come from secondary fibers and sizing agents.The fatty acids,aromatic acids and their derivatives,which may come from secondary fibers,impurities and additives,such as printing ink,plastic matters,surface active agents,were mainly existed in the white water and mixed water coming out of the mill.It was found that the mixed water contained most kinds of organic chemicals while the vacuum pumping water contained the least organic chemicals.The main chemicals contained in vacuum water were aromatic acids.There are large mounts of fatty acids,aromatic acids and theirs derivations in the wastewater of each papermaking processes,most of them are brought by the adding of secondary fiber and other additives.These organics are harmful to the environment,and difficult to be eliminated by sedimentation and flocculation.Therefore,in order to reduce the pollution of the organic pollutants in effluent wastewater,it is necessary to avoid adding phthalic acid and ester of phthalic acid.The addition of additives of long chain fatty acids and aromatic compound should be minimized in the papermaking processes.
2011, 28(4): 478-482
doi: 10.3724/SP.J.1095.2011.00505
Abstract:
The hierarchical porous aluminosilicate material was obtained by hydrothermal treatment and calcination of the precursor prepared using polystyrene spheres coated with polyelectrolyte as the template.The hierarchical porous materials were characterized by XRD,FT-IR,N2 adsorption-desorption,SEM and TEM.In addition,the influence of crystallized time on the porous structures was studied.The results show that the material contained meso-macropore with hydrothermal treatment of less than 22 h.However,the sample exhibits micro-meso-macroporous structures when the crystallized time was more than 22 h.In particular,the XRD and SEM results exhibit that the wall of macro-pore was composed of nano-ZSM-5 zeolite when the sample was crystallized for 36 h.
The hierarchical porous aluminosilicate material was obtained by hydrothermal treatment and calcination of the precursor prepared using polystyrene spheres coated with polyelectrolyte as the template.The hierarchical porous materials were characterized by XRD,FT-IR,N2 adsorption-desorption,SEM and TEM.In addition,the influence of crystallized time on the porous structures was studied.The results show that the material contained meso-macropore with hydrothermal treatment of less than 22 h.However,the sample exhibits micro-meso-macroporous structures when the crystallized time was more than 22 h.In particular,the XRD and SEM results exhibit that the wall of macro-pore was composed of nano-ZSM-5 zeolite when the sample was crystallized for 36 h.
2011, 28(4): 483-485
doi: 10.3724/SP.J.1095.2011.00433
Abstract:
Fe3+ was extracted from Fe(NO3)3 by liquid phase extraction using a mixture of bi-(2-ethylhexyl) phosphate(P204) and tetrachloride carbon.Fe(OH)3 powders were prepared through stripping precipitation method with ammonia-alcohol aqueous solution as a re-extractant and precipitator.α-Fe2O3 powders were obtained by decomposing Fe(OH)3 at an appropriate temperature and characterized by TEM,FTIR,and XRD.The results show that the P204 contents are in the oil phase,Fe3+ contents are in the water phase,and the reaction time has obvious influence on the extraction of Fe3+.Under the optimum conditions of phase volume ratio at 1:1,c(Fe3+) at 0.10 mol/L(pH=3.0),volume ratio of P204 and CCl4 as 1:3,and reaction time of 20 min,98.44% of Fe3+ is extracted.α-Fe2O3 powders with a small size and uniformity are obtained at 600℃.The optimum aging temperature and concentration of ammonia aqueous are 10.0℃ and 1:7,respectively.
Fe3+ was extracted from Fe(NO3)3 by liquid phase extraction using a mixture of bi-(2-ethylhexyl) phosphate(P204) and tetrachloride carbon.Fe(OH)3 powders were prepared through stripping precipitation method with ammonia-alcohol aqueous solution as a re-extractant and precipitator.α-Fe2O3 powders were obtained by decomposing Fe(OH)3 at an appropriate temperature and characterized by TEM,FTIR,and XRD.The results show that the P204 contents are in the oil phase,Fe3+ contents are in the water phase,and the reaction time has obvious influence on the extraction of Fe3+.Under the optimum conditions of phase volume ratio at 1:1,c(Fe3+) at 0.10 mol/L(pH=3.0),volume ratio of P204 and CCl4 as 1:3,and reaction time of 20 min,98.44% of Fe3+ is extracted.α-Fe2O3 powders with a small size and uniformity are obtained at 600℃.The optimum aging temperature and concentration of ammonia aqueous are 10.0℃ and 1:7,respectively.
2011, 28(4): 486-488
doi: 10.3724/SP.J.1095.2011.00377
Abstract:
The enantioseparation of four compounds,3-(diethylamino)-1-phenylpropan-1-ol(a),1-phenyl-3-(piperidin-1-yl) propan-1-ol(b),3-morpholino-1-p-tolypropan-1-ol(c) and 1-(4-chlorophenyl)-3-morpholinopropan-1-ol(d),obtained from asymmetry synthesis,was studied by capillary electrophoresis using α-cyclodextrin,β-cyclodextrin and β-cyclodextrin polymer as chiral selectors.With 20 kV as the separation voltage,and 30 g/L β-cyclodextrin polymer in 80 mmol/L Tris(pH=3.2) as background electrolyte solution,four chiral compounds were enantioseparated in 40 min.The enantiomeric purity of these four chiral compounds was determined according to the ratio of peak area with RSD no more than 1.5%.
The enantioseparation of four compounds,3-(diethylamino)-1-phenylpropan-1-ol(a),1-phenyl-3-(piperidin-1-yl) propan-1-ol(b),3-morpholino-1-p-tolypropan-1-ol(c) and 1-(4-chlorophenyl)-3-morpholinopropan-1-ol(d),obtained from asymmetry synthesis,was studied by capillary electrophoresis using α-cyclodextrin,β-cyclodextrin and β-cyclodextrin polymer as chiral selectors.With 20 kV as the separation voltage,and 30 g/L β-cyclodextrin polymer in 80 mmol/L Tris(pH=3.2) as background electrolyte solution,four chiral compounds were enantioseparated in 40 min.The enantiomeric purity of these four chiral compounds was determined according to the ratio of peak area with RSD no more than 1.5%.
