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2010 Volume 27 Issue 5
2010, 27(5): 497-504
doi: 10.3724/SP.J.1095.2010.90407
Abstract:
The authors briefly summarized the recent progress of benzo[b]thiophene derivatives used for organic field-effect transistors(OFET),in which two families:ladder-type and star-shape compounds were presented.The synthetic approaches and the properties of polycyclic hydrocarbons for application in OFET were introduced.Benzo[b]thiophene derivatives will become promising candidates as the active materials with high performance in the application of organic electronics.
The authors briefly summarized the recent progress of benzo[b]thiophene derivatives used for organic field-effect transistors(OFET),in which two families:ladder-type and star-shape compounds were presented.The synthetic approaches and the properties of polycyclic hydrocarbons for application in OFET were introduced.Benzo[b]thiophene derivatives will become promising candidates as the active materials with high performance in the application of organic electronics.
2010, 27(5): 505-509
doi: 10.3724/SP.J.1095.2010.90447
Abstract:
Polysaccharide surfaces were constructed from carrageenan and poly (diallyldimethylammonium chloride)(PDDA) via layer-by-layer assembly technique. The adsorption of bovine serum albumin(BSA),an ellipsoidal model protein,on the surface of the multilayers was studied in detail by means of a quartz crystal microbalance with dissipation monitoring(QCM-D).Four carrageenans with different charge densities were investigated,and the amount of the carrageenan assembled was found to decrease with the increase of the charge density.When BSA was adsorbed on the PDDA surface,the dissipation factor(△D) was small,indicating that BSA lay down on the surface to form a thin layer.When BSA was adsorbed to the ι-carrageenan (IC) surface,both the QCM frequency shifts(△F) and the dissipation factor △D were larger,suggesting that BSA stood on the carrageenan surface to form a thicker layer.In addition,it was found that both the amount of adsorption and the packing of BSA on the carrageenan surface depended on the charge density and the surface roughness of the carrageenan substrate.
Polysaccharide surfaces were constructed from carrageenan and poly (diallyldimethylammonium chloride)(PDDA) via layer-by-layer assembly technique. The adsorption of bovine serum albumin(BSA),an ellipsoidal model protein,on the surface of the multilayers was studied in detail by means of a quartz crystal microbalance with dissipation monitoring(QCM-D).Four carrageenans with different charge densities were investigated,and the amount of the carrageenan assembled was found to decrease with the increase of the charge density.When BSA was adsorbed on the PDDA surface,the dissipation factor(△D) was small,indicating that BSA lay down on the surface to form a thin layer.When BSA was adsorbed to the ι-carrageenan (IC) surface,both the QCM frequency shifts(△F) and the dissipation factor △D were larger,suggesting that BSA stood on the carrageenan surface to form a thicker layer.In addition,it was found that both the amount of adsorption and the packing of BSA on the carrageenan surface depended on the charge density and the surface roughness of the carrageenan substrate.
2010, 27(5): 510-513
doi: 10.3724/SP.J.1095.2010.90431
Abstract:
Helical polyaniline nanofibers were prepared by a facilel interface polymerization method with chiral regents D-and L-camphorsulfonic acid(D-and L-CSA) as dopants and conformation inducer.The as-prepared helical polyaniline nanofibers were characterized by FESEM,TEM,FTIR,UV-Vis spectroscopies.The results show that relatively uniform polyaniline nanofibers with a helical conformation and higher ratio of length to diameter(6:1~12:1) could be readily obtained by means of this method,the average diameter and the lengths were about 50 nm and in a range of 300~600 nm,respectively.The helical polyaniline nanofibers exist in more expanded coil molecular conformation in aqueous solution and show reversible doping-dedoping nature along with the change of pH value of solution.Cyclic voltammetry tests show that the helical polyaniline nanofibers exhibit good electrochemical activity in a 0.5 mol/L HCl aqueous solution.
Helical polyaniline nanofibers were prepared by a facilel interface polymerization method with chiral regents D-and L-camphorsulfonic acid(D-and L-CSA) as dopants and conformation inducer.The as-prepared helical polyaniline nanofibers were characterized by FESEM,TEM,FTIR,UV-Vis spectroscopies.The results show that relatively uniform polyaniline nanofibers with a helical conformation and higher ratio of length to diameter(6:1~12:1) could be readily obtained by means of this method,the average diameter and the lengths were about 50 nm and in a range of 300~600 nm,respectively.The helical polyaniline nanofibers exist in more expanded coil molecular conformation in aqueous solution and show reversible doping-dedoping nature along with the change of pH value of solution.Cyclic voltammetry tests show that the helical polyaniline nanofibers exhibit good electrochemical activity in a 0.5 mol/L HCl aqueous solution.
2010, 27(5): 514-517
doi: 10.3724/SP.J.1095.2010.90492
Abstract:
Brominated natural rubber(BNR) with different bromine content was prepared in the latex phase.Fourier transform infrared spectroscopy(FTIR) and 1H NMR spectroscopy were applied to investigated the microstructures of BNR from latex.Scanning electron microscope(SEM) was adopted to observe the morphology of BNR products,and the solubility and nitrogen content of BNR products with different bromine content were studied.FTIR analysis shows that bromination substitution and addition occur during the brominatio of NR latex.1H NMR analysis confirms the addition of C=C group and the bromination substitution of methylene and methyl groups.Bromine content has an obvious effect on the morphology of BNR products.With the increment of bromine content,BNR product is getting hardened and crisp,easier to be powdery and the dimension of particles gradually decreases.The solubility sequence of BNR product in different solvents is as follows:benzene,carbon tetrachloride < toluene,xylene < tetrahydrofuran < chloroform < cyclohexanone; and the solubility of BNR in the same solvent increases with the increment of bromine content. Nitrogen content of BNR products decreases with the increment of bromine content.Nitrogen content decreases to 0.10% when bromine content is 42%.
Brominated natural rubber(BNR) with different bromine content was prepared in the latex phase.Fourier transform infrared spectroscopy(FTIR) and 1H NMR spectroscopy were applied to investigated the microstructures of BNR from latex.Scanning electron microscope(SEM) was adopted to observe the morphology of BNR products,and the solubility and nitrogen content of BNR products with different bromine content were studied.FTIR analysis shows that bromination substitution and addition occur during the brominatio of NR latex.1H NMR analysis confirms the addition of C=C group and the bromination substitution of methylene and methyl groups.Bromine content has an obvious effect on the morphology of BNR products.With the increment of bromine content,BNR product is getting hardened and crisp,easier to be powdery and the dimension of particles gradually decreases.The solubility sequence of BNR product in different solvents is as follows:benzene,carbon tetrachloride < toluene,xylene < tetrahydrofuran < chloroform < cyclohexanone; and the solubility of BNR in the same solvent increases with the increment of bromine content. Nitrogen content of BNR products decreases with the increment of bromine content.Nitrogen content decreases to 0.10% when bromine content is 42%.
2010, 27(5): 518-522
doi: 10.3724/SP.J.1095.2010.90470
Abstract:
The molecularly imprinted microspheres(MIMs-IL) were synthesized with hydroquinone as template molecules,α-acrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker by suspension polymerization in two-phase system of ionic liquid-based aqueous.The MIMs-IL was characterized by FTIR and its selective recognition was evaluated by adsorption experiments.[Bmim]PF6 was selected from three different types of IL. Compared with that of the molecularly imprinted microspheres(MIMs-Or) prepared in two-phase system of chloroform-aqueous,the yield of MIMs-IL,70.8% is obviously higher than that of MIMs-Or,48.7%.The recognition adsorption of MIMs-IL for hydroquinone in water solution is higher than that of MIMs-Or.Moreover,the results of thermodynamics and kinetics of the recognition adsorption of MIMs-IL show that the saturation adsorption amount was achieved in 12 h,and MIMs-IL displayed a 2.67-fold increase in adsorption amount for 0.50 g/L hydroquinone water solution compared to its none molecularly imprinted microspheres(nMIMs-IL).
The molecularly imprinted microspheres(MIMs-IL) were synthesized with hydroquinone as template molecules,α-acrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker by suspension polymerization in two-phase system of ionic liquid-based aqueous.The MIMs-IL was characterized by FTIR and its selective recognition was evaluated by adsorption experiments.[Bmim]PF6 was selected from three different types of IL. Compared with that of the molecularly imprinted microspheres(MIMs-Or) prepared in two-phase system of chloroform-aqueous,the yield of MIMs-IL,70.8% is obviously higher than that of MIMs-Or,48.7%.The recognition adsorption of MIMs-IL for hydroquinone in water solution is higher than that of MIMs-Or.Moreover,the results of thermodynamics and kinetics of the recognition adsorption of MIMs-IL show that the saturation adsorption amount was achieved in 12 h,and MIMs-IL displayed a 2.67-fold increase in adsorption amount for 0.50 g/L hydroquinone water solution compared to its none molecularly imprinted microspheres(nMIMs-IL).
2010, 27(5): 523-527
doi: 10.3724/SP.J.1095.2010.90345
Abstract:
To develop a novel inhibitor of Mycobacterium tuberculosis,a new compound 5-[β-(2-hydroxylphenyl)propynoylamic]-5-deoxyadenosine was synthesized from the starting material of 2-iodine phenol via a series of reactions such as Sonogashira and condensation reactions.The experimental conditions were optimized.The structure of the compound was determined by 1H NMR,13C NMR,IR and LC/MS.
To develop a novel inhibitor of Mycobacterium tuberculosis,a new compound 5-[β-(2-hydroxylphenyl)propynoylamic]-5-deoxyadenosine was synthesized from the starting material of 2-iodine phenol via a series of reactions such as Sonogashira and condensation reactions.The experimental conditions were optimized.The structure of the compound was determined by 1H NMR,13C NMR,IR and LC/MS.
2010, 27(5): 528-532
doi: 10.3724/SP.J.1095.2010.90520
Abstract:
Xanthono-pyridine(2) was synthesized by means of Ullmann method from o-iodobenzoic acid and 8-hydroxyquinoline;then compound 2 was treated with methyl iodide,ethyl iodide to afford quaternary ammonium salts 3a and 3b,respectively. Their structures were confirmed by IR,NMR,MS and elemental analysis. The two target compounds' cytotoxic activities against four human cancer cell lines including A2780 (ovarian cancer), Hela(cervical cancer), SPC-A(liver cancer) and KB(oral epithelial carcinoma),were evaluated in vitro by MTT method,the results show that the activities of both salts 3a and 3b were better than that of the positive control 5-Fu. Ethidium bromide displacement assay showed that the apparent binding constants(Kapp) of compound 3a and 3b with CT-DNA(calf thymus) were 3.91 × 105 L/mol and 2.72 × 105 L/mol, respectively, which suggests that their anti-cancer capabilities might be associated with their interactions with DNA. Their inhibitory activities on acetylcholinesterase(AChE) and butyrylcholinersterase(BuChE) were studied as well. The two compounds showed better and almost equivalent inhibitory activity on AChE. The IC50 values reach μmol/L level, which are close to that of Galantamine·HBr;enzyme kinetic study indicates that the type of their inhibition on AChE was non-competitive action.
Xanthono-pyridine(2) was synthesized by means of Ullmann method from o-iodobenzoic acid and 8-hydroxyquinoline;then compound 2 was treated with methyl iodide,ethyl iodide to afford quaternary ammonium salts 3a and 3b,respectively. Their structures were confirmed by IR,NMR,MS and elemental analysis. The two target compounds' cytotoxic activities against four human cancer cell lines including A2780 (ovarian cancer), Hela(cervical cancer), SPC-A(liver cancer) and KB(oral epithelial carcinoma),were evaluated in vitro by MTT method,the results show that the activities of both salts 3a and 3b were better than that of the positive control 5-Fu. Ethidium bromide displacement assay showed that the apparent binding constants(Kapp) of compound 3a and 3b with CT-DNA(calf thymus) were 3.91 × 105 L/mol and 2.72 × 105 L/mol, respectively, which suggests that their anti-cancer capabilities might be associated with their interactions with DNA. Their inhibitory activities on acetylcholinesterase(AChE) and butyrylcholinersterase(BuChE) were studied as well. The two compounds showed better and almost equivalent inhibitory activity on AChE. The IC50 values reach μmol/L level, which are close to that of Galantamine·HBr;enzyme kinetic study indicates that the type of their inhibition on AChE was non-competitive action.
2010, 27(5): 533-538
doi: 10.3724/SP.J.1095.2010.90454
Abstract:
Thirteen new 2-aryloxy-3-phenyl-3, 5, 6, 7-tetrahydro-4H-cyclopenta[4, 5]thieno[2, 3-d]pyrimidin-4-ones were synthesized in 63%~78% yields via the aza-Wittig reaction of (4,5,6-trihydrocyclopentathiophen-2-ylimino) (triphenyl) phosphorane with phenyl iso-cyanate, and subsequent reaction with phenols. Their structures were confirmed by IR,1H NMR, MS and elemental analysis. The bacteriostatic activities of the new compounds were tested. The results show that bacteriostatic activities of the compounds against fungus (Penicillium citrinum Thom) are better than those against bacteria.
Thirteen new 2-aryloxy-3-phenyl-3, 5, 6, 7-tetrahydro-4H-cyclopenta[4, 5]thieno[2, 3-d]pyrimidin-4-ones were synthesized in 63%~78% yields via the aza-Wittig reaction of (4,5,6-trihydrocyclopentathiophen-2-ylimino) (triphenyl) phosphorane with phenyl iso-cyanate, and subsequent reaction with phenols. Their structures were confirmed by IR,1H NMR, MS and elemental analysis. The bacteriostatic activities of the new compounds were tested. The results show that bacteriostatic activities of the compounds against fungus (Penicillium citrinum Thom) are better than those against bacteria.
2010, 27(5): 539-543
doi: 10.3724/SP.J.1095.2010.90435
Abstract:
2,4,6-Triarylpyrylium salts were synthesized with aromatic aldehydes and aromatic ketones as starting materials.We succeeded in the conversion of these salts with hydroxylamine hydrochloride in water and synthesized the 3,5-diarylisoxazole derivatives under microwave irradiation.In comparison with literature method,the microwave approach shows the salient features of rapid reaction rates and significant energy saving,clean reaction conditions,enhancement in chemical yield,and nonuse of perchloric acid(70%),which will result in cost saving and minimize safety concerns in the organic laboratory.In addition,the use of aqueous reaction conditions results in simple,environmentally friendly procedures.This rapid and easy technique coupled with water medium may contribute to the dream of Green Technology.The optimum reaction conditions were selected(P=600 W,time=8 min,yield 83%) and twelve compounds were synthesized via this procedure.The structures of the products were confirmed by elemental analysis,MS and 1H NMR spectroscopy.
2,4,6-Triarylpyrylium salts were synthesized with aromatic aldehydes and aromatic ketones as starting materials.We succeeded in the conversion of these salts with hydroxylamine hydrochloride in water and synthesized the 3,5-diarylisoxazole derivatives under microwave irradiation.In comparison with literature method,the microwave approach shows the salient features of rapid reaction rates and significant energy saving,clean reaction conditions,enhancement in chemical yield,and nonuse of perchloric acid(70%),which will result in cost saving and minimize safety concerns in the organic laboratory.In addition,the use of aqueous reaction conditions results in simple,environmentally friendly procedures.This rapid and easy technique coupled with water medium may contribute to the dream of Green Technology.The optimum reaction conditions were selected(P=600 W,time=8 min,yield 83%) and twelve compounds were synthesized via this procedure.The structures of the products were confirmed by elemental analysis,MS and 1H NMR spectroscopy.
2010, 27(5): 544-548
doi: 10.3724/SP.J.1095.2010.90348
Abstract:
The degradation efficiency,influencing factors and kinetics of SF Blue dye in UV/H2O2 system were investigated.The results show that UV/H2O2 has a high activity on the dye degradation.The degradation ratio at 60 min is 98% for the system containing 0.5 mL 5% H2O2 in 150 mL 100 mg/L dye solution.The photodecomposition reaction of the dye is accompanied with photooxidative degradation.The results also show that the photooxidative degradation of the dye in UV/H2O2 system is a first-order reaction with an activation energy of 5.17 kJ/mol and a pre-exponential factor of 0.168 min-1 the photodecomposition of the dye in UV system is also a first-order reaction with an activation energy of 16.9 kJ/mol and a pre-exponential factor of 1.04 min-1. In addition,the best degradation efficiency of the dye could be achieved under a strong alkaline condition with initial pH of the dye solution around 12.
The degradation efficiency,influencing factors and kinetics of SF Blue dye in UV/H2O2 system were investigated.The results show that UV/H2O2 has a high activity on the dye degradation.The degradation ratio at 60 min is 98% for the system containing 0.5 mL 5% H2O2 in 150 mL 100 mg/L dye solution.The photodecomposition reaction of the dye is accompanied with photooxidative degradation.The results also show that the photooxidative degradation of the dye in UV/H2O2 system is a first-order reaction with an activation energy of 5.17 kJ/mol and a pre-exponential factor of 0.168 min-1 the photodecomposition of the dye in UV system is also a first-order reaction with an activation energy of 16.9 kJ/mol and a pre-exponential factor of 1.04 min-1. In addition,the best degradation efficiency of the dye could be achieved under a strong alkaline condition with initial pH of the dye solution around 12.
2010, 27(5): 549-552
doi: 10.3724/SP.J.1095.2010.90439
Abstract:
The novel catalysts of Cu supported on ZnO,MgO modified with KF were prepared by the conventional impregnation method,and applied for the first time to the Heck reactions of iodobenzene with n-butyl acrylate as a model reaction.The results indicate that little conversion of iodobenzene was observed on unmodified carrier supported catalysts;and a conversion of 100% and a selectivity of above 98% to trans-isomers were found over 10% Cu/5% KF/ZnO,20% Cu/10% KF/ZnO.The conversion of p-nitrobromobenzene could reach 34.3% in the Heck reaction with n-butyl acrylate catalyzed by 10% Cu/5% KF/ZnO.The modified carrier supported catalyst can be reused after regeneration without significant loss in catalytic activity in four cycles,for example,the conversion of iodobenzene over 20% Cu/10% KF/ZnO was found to be 65.4% in four cycles.The XRD patterns of the catalysts show that the content of CuO on the surface of the catalysts was raised with addition of modifying agent so as to increase the activity of catalysts.
The novel catalysts of Cu supported on ZnO,MgO modified with KF were prepared by the conventional impregnation method,and applied for the first time to the Heck reactions of iodobenzene with n-butyl acrylate as a model reaction.The results indicate that little conversion of iodobenzene was observed on unmodified carrier supported catalysts;and a conversion of 100% and a selectivity of above 98% to trans-isomers were found over 10% Cu/5% KF/ZnO,20% Cu/10% KF/ZnO.The conversion of p-nitrobromobenzene could reach 34.3% in the Heck reaction with n-butyl acrylate catalyzed by 10% Cu/5% KF/ZnO.The modified carrier supported catalyst can be reused after regeneration without significant loss in catalytic activity in four cycles,for example,the conversion of iodobenzene over 20% Cu/10% KF/ZnO was found to be 65.4% in four cycles.The XRD patterns of the catalysts show that the content of CuO on the surface of the catalysts was raised with addition of modifying agent so as to increase the activity of catalysts.
2010, 27(5): 553-557
doi: 10.3724/SP.J.1095.2010.90440
Abstract:
Glutamic acid(Glu) was intercalated into ZnAl layered double hydroxides(ZnAl-LDH) via the ion-exchange method to form Glu/ZnAl-LDH compounds,and the influence of exchange time on the structure of Glu/ZnAl-LDH was systematically investigated by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),transmission electron microscopy(TEM),thermo-gravimetry(TG) and differential thermal analysis(DTA) techniques.It was found that when the exchange time was one day,the crystallinity of Glu/ZnAl-LDH compounds was high and Glu was intercalated vertically into the ZnAl-LDH sheets,and Glu in the layers reached exchange equilibrium at this moment.When the exchange time was 2 days,part of Glu was intercalated horizontally.When the exchange time was further extended,the strucutre of ZnAl-LDH would be partially collapsed.In addition,the hexagonal shape of ZnAl-LDH compounds would be dissolved partially in the acid solution.Furthermore,the thermal stability of Glu would be increased dramatically when Glu was intercalated into ZnAl-LDH compounds,hence,ZnAl-LDH could be used as the excellent carrier and storage of biomaterial.
Glutamic acid(Glu) was intercalated into ZnAl layered double hydroxides(ZnAl-LDH) via the ion-exchange method to form Glu/ZnAl-LDH compounds,and the influence of exchange time on the structure of Glu/ZnAl-LDH was systematically investigated by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),transmission electron microscopy(TEM),thermo-gravimetry(TG) and differential thermal analysis(DTA) techniques.It was found that when the exchange time was one day,the crystallinity of Glu/ZnAl-LDH compounds was high and Glu was intercalated vertically into the ZnAl-LDH sheets,and Glu in the layers reached exchange equilibrium at this moment.When the exchange time was 2 days,part of Glu was intercalated horizontally.When the exchange time was further extended,the strucutre of ZnAl-LDH would be partially collapsed.In addition,the hexagonal shape of ZnAl-LDH compounds would be dissolved partially in the acid solution.Furthermore,the thermal stability of Glu would be increased dramatically when Glu was intercalated into ZnAl-LDH compounds,hence,ZnAl-LDH could be used as the excellent carrier and storage of biomaterial.
2010, 27(5): 558-562
doi: 10.3724/SP.J.1095.2010.90436
Abstract:
Nonionic surfactant of special phenylethyl phenol formaldehyde resin polyoxyethylene ether and anion surfactant of calcium dodecylbenzene sulfonate were used as mixed surfactants with mass ratio at 3 to 7,with chlorpyrifos xylene solusion at 75% mass percentage as oil phase,to form chlorpyrifos microemulsion.The transparent temperature region of the microemulsion was determained by turbidness phenomena when temerpature was slowly raised or desreased.Effects of electrolytes and pH on the transparent temperature region of chlorpyrifos microemulsion were investigated.The results show that the addition of electrolyte and the surfactant content could influence on the transparent temperature region of chlorpyrifos microemulsion.The upper limit of transparent temperature of the systems gradually decreased with the increasing of cationic content,but the change of the lower limit of transparent temperature was relatively small.The upper limit of transparent temperature increased firstly with the increasing of anionic content,and then decreased.In both strong acid and strong base solutions,the upper limit of transparent temperature decreased,with a maximum value achieved at weak acid medium.The lower limit of transparent temperature region increased slightly with the increase of pH value.
Nonionic surfactant of special phenylethyl phenol formaldehyde resin polyoxyethylene ether and anion surfactant of calcium dodecylbenzene sulfonate were used as mixed surfactants with mass ratio at 3 to 7,with chlorpyrifos xylene solusion at 75% mass percentage as oil phase,to form chlorpyrifos microemulsion.The transparent temperature region of the microemulsion was determained by turbidness phenomena when temerpature was slowly raised or desreased.Effects of electrolytes and pH on the transparent temperature region of chlorpyrifos microemulsion were investigated.The results show that the addition of electrolyte and the surfactant content could influence on the transparent temperature region of chlorpyrifos microemulsion.The upper limit of transparent temperature of the systems gradually decreased with the increasing of cationic content,but the change of the lower limit of transparent temperature was relatively small.The upper limit of transparent temperature increased firstly with the increasing of anionic content,and then decreased.In both strong acid and strong base solutions,the upper limit of transparent temperature decreased,with a maximum value achieved at weak acid medium.The lower limit of transparent temperature region increased slightly with the increase of pH value.
2010, 27(5): 563-566
doi: 10.3724/SP.J.1095.2010.90448
Abstract:
The solubility improvement of dexamethasone acetate by tetramethyl substituted cucurbit[6]urils(TMeQ[6]) was studied with the micro porous filter membrane separation technique,and the solid inclusion complex of TMeQ[6] and dexamethasone acetate was analyzed with the method of DTA.The results show that TMeQ[6] was able to increase the solubility of dexamethasone acetate,and the solubilization improvement could reach 4~17-fold when the concentration of TMeQ[6] increased from 0.04 to 0.28 mmol/L.While the temperature increased from 10℃ to 70℃,the solubilization decreased in the range of 10~30℃,and then leveled off in the range of 40~70℃.At the same time,the solid inclusion complex of dexamethasone acetate with TMeQ[6] was prepared through cosolvent method,and its host-guest interaction was studied by DTA.
The solubility improvement of dexamethasone acetate by tetramethyl substituted cucurbit[6]urils(TMeQ[6]) was studied with the micro porous filter membrane separation technique,and the solid inclusion complex of TMeQ[6] and dexamethasone acetate was analyzed with the method of DTA.The results show that TMeQ[6] was able to increase the solubility of dexamethasone acetate,and the solubilization improvement could reach 4~17-fold when the concentration of TMeQ[6] increased from 0.04 to 0.28 mmol/L.While the temperature increased from 10℃ to 70℃,the solubilization decreased in the range of 10~30℃,and then leveled off in the range of 40~70℃.At the same time,the solid inclusion complex of dexamethasone acetate with TMeQ[6] was prepared through cosolvent method,and its host-guest interaction was studied by DTA.
2010, 27(5): 567-571
doi: 10.3724/SP.J.1095.2010.90410
Abstract:
The crystal growth of CaCO3 with dodecylbenzenesulfonate sodium(SDBS) and L-histidine as growth regulators were studied were characterized with powder X-ray diffraction and infrared spectrometry.We also used scanning electron microscopy to analyze the crystal shapes of generated CaCO3 in order to study the effect of surfactant concentration,temperature and solvent composition on the crystal morphology and shape of CaCO3.The results show that under experimental conditions,the concentration of surfactant SDBS has no effect on the crystal morphology of CaCO3,but affect the shapes of the crystals,in the mean time,the temperature and solvent composition greatly affect the crystal morphology and crystal shape of CaCO3.
The crystal growth of CaCO3 with dodecylbenzenesulfonate sodium(SDBS) and L-histidine as growth regulators were studied were characterized with powder X-ray diffraction and infrared spectrometry.We also used scanning electron microscopy to analyze the crystal shapes of generated CaCO3 in order to study the effect of surfactant concentration,temperature and solvent composition on the crystal morphology and shape of CaCO3.The results show that under experimental conditions,the concentration of surfactant SDBS has no effect on the crystal morphology of CaCO3,but affect the shapes of the crystals,in the mean time,the temperature and solvent composition greatly affect the crystal morphology and crystal shape of CaCO3.
2010, 27(5): 572-578
doi: 10.3724/SP.J.1095.2010.90451
Abstract:
The surface tension of the mixtures of cationic-anionic hydrocarbon-fluorocarbon surfactants composed of octyltriethylammonium bromide (C8H17N(CH2CH3)3Br, C8NE) and sodium perfluorobutane sulfonate (C4F9SO3Na, C4F) with different molar ratios was measured. The cmc,γcmc, total adsorption amount, the compositions of surface adsorption layers at different surface tension values and the micell composition at cmc calculated by means of Gibbs-Duhem equation were obtained. The molecular interaction parameter βm and the micell composition after cmc were estimated via the regular solution theory. It shows that the cmc of each of C8NE-C4F mixtures was far smaller than that of individual component, which is consistent with the large negative value of βm and thus there are strong molecular interactions in micelle. However, the γcmc values of C8NE-C4F mixtures were not changed greatly as expected when compared with single C4F(γcmcwas decreased by 24 mN/m), which might be attributed to the asymmetry between C8NE-C4F chains and some C8NE chains partially bending and covering the terminal CF3 group of C4F on the surface. In the surface adsorption layer,the fluorocarbon surfactant was rich-collected compared with the bulk solution. Even for those systems with C8NE in greatly excess, the composition of surface adsorption layer was just around equimolar; while for those systems with C4F in excess, the content of C4F in the surface adsorption layer was a little larger than that in solution.The composition of surface adsorption layer moved further to the C4F side with the decrease of surface tension. The micell composition at cmc was favorable to the formation of C4F-richer micelle with the increase of C4F content in bulk systems. For those systems with C8NE in great excess, the micell composition at cmc was around equimolar. The micell composition after cmc was approximately equimolar, which might be due to the predominant electrostatic interactions. It is consistent with the phenomenon that the mixture tended to precipitate when the concentration exceeded a certain amount after cmc.
The surface tension of the mixtures of cationic-anionic hydrocarbon-fluorocarbon surfactants composed of octyltriethylammonium bromide (C8H17N(CH2CH3)3Br, C8NE) and sodium perfluorobutane sulfonate (C4F9SO3Na, C4F) with different molar ratios was measured. The cmc,γcmc, total adsorption amount, the compositions of surface adsorption layers at different surface tension values and the micell composition at cmc calculated by means of Gibbs-Duhem equation were obtained. The molecular interaction parameter βm and the micell composition after cmc were estimated via the regular solution theory. It shows that the cmc of each of C8NE-C4F mixtures was far smaller than that of individual component, which is consistent with the large negative value of βm and thus there are strong molecular interactions in micelle. However, the γcmc values of C8NE-C4F mixtures were not changed greatly as expected when compared with single C4F(γcmcwas decreased by 24 mN/m), which might be attributed to the asymmetry between C8NE-C4F chains and some C8NE chains partially bending and covering the terminal CF3 group of C4F on the surface. In the surface adsorption layer,the fluorocarbon surfactant was rich-collected compared with the bulk solution. Even for those systems with C8NE in greatly excess, the composition of surface adsorption layer was just around equimolar; while for those systems with C4F in excess, the content of C4F in the surface adsorption layer was a little larger than that in solution.The composition of surface adsorption layer moved further to the C4F side with the decrease of surface tension. The micell composition at cmc was favorable to the formation of C4F-richer micelle with the increase of C4F content in bulk systems. For those systems with C8NE in great excess, the micell composition at cmc was around equimolar. The micell composition after cmc was approximately equimolar, which might be due to the predominant electrostatic interactions. It is consistent with the phenomenon that the mixture tended to precipitate when the concentration exceeded a certain amount after cmc.
2010, 27(5): 579-584
doi: 10.3724/SP.J.1095.2010.90460
Abstract:
Ni-P-mCMC/mCS bipolar membrane(BPM) was prepared from carboxymethyl cellulose(CMC) modified with phosphorylated agent as a cation exchange layer and chitosan(CS) modified with glutaraldehyde(GA) as an anion exchange layer.The electrolysis cell was constituted by Ni-P-mCMC/mCS BPM as a septum for electro-generating furfural alcohol(in the cathode room) and furoic acid(in the anode room).The experiment results show that H+ generated by the BPM moves into the cathode room from the interface layer of the Ni-P-mCMC/mCS BPM to promote the electro-reduction of furfural for generating furfuryl alcohol;OH- moves into the anode room to combine with H+ produced by electro-oxygenation of furfural to generate furoic acid and improve the forward reaction speed.The electrolysis efficiency was up to 82.4% in the cathode room and 77.4% in the anode room at 30℃ when the current density was 2.5 × 10-2 A/cm2.
Ni-P-mCMC/mCS bipolar membrane(BPM) was prepared from carboxymethyl cellulose(CMC) modified with phosphorylated agent as a cation exchange layer and chitosan(CS) modified with glutaraldehyde(GA) as an anion exchange layer.The electrolysis cell was constituted by Ni-P-mCMC/mCS BPM as a septum for electro-generating furfural alcohol(in the cathode room) and furoic acid(in the anode room).The experiment results show that H+ generated by the BPM moves into the cathode room from the interface layer of the Ni-P-mCMC/mCS BPM to promote the electro-reduction of furfural for generating furfuryl alcohol;OH- moves into the anode room to combine with H+ produced by electro-oxygenation of furfural to generate furoic acid and improve the forward reaction speed.The electrolysis efficiency was up to 82.4% in the cathode room and 77.4% in the anode room at 30℃ when the current density was 2.5 × 10-2 A/cm2.
2010, 27(5): 585-589
doi: 10.3724/SP.J.1095.2010.90413
Abstract:
An ultrasensitive resonance rayleigh scattering(RRS) method for the determination of trace octreotide was developed.The determination of octreotide in an octreotide-methyl red system via RRS was studied comprehensively.In a pH=3.78 B-R buffer solution,the RRS intensity is enhanced obviously in the range of 280~370 nm as octreotide associates with methyl red.The strongest △IRRS is at 310 nm.The RRS intensitiy of octreotide is proportional to the concentration of octreotide over the range of 0~0.54 mg/L,the detection limit for the octreotide(3σ) is 3.6 μg/L under optimum conditions.The method was applied to the determination of octreotide in synthetic samples with the recovery of 98.3%~100.7%.Measurements of the commercial injection samples also gave satisfactory results which were in good agreement with those obtained using high performance liquid chromatography(HPLC) method.
An ultrasensitive resonance rayleigh scattering(RRS) method for the determination of trace octreotide was developed.The determination of octreotide in an octreotide-methyl red system via RRS was studied comprehensively.In a pH=3.78 B-R buffer solution,the RRS intensity is enhanced obviously in the range of 280~370 nm as octreotide associates with methyl red.The strongest △IRRS is at 310 nm.The RRS intensitiy of octreotide is proportional to the concentration of octreotide over the range of 0~0.54 mg/L,the detection limit for the octreotide(3σ) is 3.6 μg/L under optimum conditions.The method was applied to the determination of octreotide in synthetic samples with the recovery of 98.3%~100.7%.Measurements of the commercial injection samples also gave satisfactory results which were in good agreement with those obtained using high performance liquid chromatography(HPLC) method.
2010, 27(5): 590-593
doi: 10.3724/SP.J.1095.2010.90529
Abstract:
A pretreatment method was developed based on solid phase extraction(SPE) and applied to determine the residual pyrimethanil and fluazifop-butyl in green onion,scallion and onion by gas chromatography-mass spectrometry(GC-MS).The samples were extracted from homogenized tissue with acetonitrile,separated with liquid-liquid partition.The supernatants were purified by SPE(Envi-18 and Florisil columns) prior to the GC-MS analysis.Determination was performed in a selected ion monitoring(SIM) mode and external standard method was used in the quantification.The method was convenient and rapid after investigating the conditions of pretreatment and determination.Under the optimal conditions,the detection limits of pesticides by the method(S/N=10) were under 0.01 mg/kg.Tests for recovery were carried out by addition of standard at a concentration of 0.01~0.2 mg/kg,the recoveries of pyrimethanil and fluazifop-butyl were 81.4%~94.6% and 107%~129% with relative standard deviations of 3.3%~11% and 4.0%~9.7%,respectively.
A pretreatment method was developed based on solid phase extraction(SPE) and applied to determine the residual pyrimethanil and fluazifop-butyl in green onion,scallion and onion by gas chromatography-mass spectrometry(GC-MS).The samples were extracted from homogenized tissue with acetonitrile,separated with liquid-liquid partition.The supernatants were purified by SPE(Envi-18 and Florisil columns) prior to the GC-MS analysis.Determination was performed in a selected ion monitoring(SIM) mode and external standard method was used in the quantification.The method was convenient and rapid after investigating the conditions of pretreatment and determination.Under the optimal conditions,the detection limits of pesticides by the method(S/N=10) were under 0.01 mg/kg.Tests for recovery were carried out by addition of standard at a concentration of 0.01~0.2 mg/kg,the recoveries of pyrimethanil and fluazifop-butyl were 81.4%~94.6% and 107%~129% with relative standard deviations of 3.3%~11% and 4.0%~9.7%,respectively.
2010, 27(5): 594-599
doi: 10.3724/SP.J.1095.2010.90516
Abstract:
In order to efficiently make use of visible light and enhance photocatalytic activity,the rutile crystal TiO2 catalysts which could utilize visible light were obtained by heat-treated method.The damage of BSA under the visible light irradiation in the presence of heat-treated anatase TiO2 was investigated by means of UV-Vis and fluorescence spectroscopies.The photocatalytic activity of the heat-treated TiO2 was compared with that of the untreated one.In addition,the influences of irradiation time,TiO2 addition dose and irradiation power on the damage of BSA molecule were studied.The results show that the damage of BSA under the visible light irradiation was achieved in the presence of heat-treated anatase TiO2.The photocatalytic activity of heat-treated TiO2 was also better than that of the untreated one.The obvious hyperchromic effect in UV-Vis spectra and the fluorescence quenching in fluorescence spectra were both observed,which resulted from the exposure of aromatic heterocycle residues of tryptophane and tyrosine.Moreover,the damage degree of tyrosine residues was greater than tryptophan residues,which was proved with synchronous fluorescence spectra.For a BSA solution of 1.0×10-5 mol/L at 25℃,the damage of BSA was aggravated with the increase of the irradiation time,TiO2 addition dose and the irradiation power.They are of significance to the study on the application of scavenger and inactivator for some virus.
In order to efficiently make use of visible light and enhance photocatalytic activity,the rutile crystal TiO2 catalysts which could utilize visible light were obtained by heat-treated method.The damage of BSA under the visible light irradiation in the presence of heat-treated anatase TiO2 was investigated by means of UV-Vis and fluorescence spectroscopies.The photocatalytic activity of the heat-treated TiO2 was compared with that of the untreated one.In addition,the influences of irradiation time,TiO2 addition dose and irradiation power on the damage of BSA molecule were studied.The results show that the damage of BSA under the visible light irradiation was achieved in the presence of heat-treated anatase TiO2.The photocatalytic activity of heat-treated TiO2 was also better than that of the untreated one.The obvious hyperchromic effect in UV-Vis spectra and the fluorescence quenching in fluorescence spectra were both observed,which resulted from the exposure of aromatic heterocycle residues of tryptophane and tyrosine.Moreover,the damage degree of tyrosine residues was greater than tryptophan residues,which was proved with synchronous fluorescence spectra.For a BSA solution of 1.0×10-5 mol/L at 25℃,the damage of BSA was aggravated with the increase of the irradiation time,TiO2 addition dose and the irradiation power.They are of significance to the study on the application of scavenger and inactivator for some virus.
2010, 27(5): 600-605
doi: 10.3724/SP.J.1095.2010.90482
Abstract:
The mechanism of the interaction between bovine serum albumin(BSA) and pyrano[4,3-b] pyran derivative,2-amino-7-methyl-4-(4-nitrophenyl)-5-oxo-4,5-dihydropyrano[4,3-b] pyran-3-carbonitrile,was studied by means of fluorescence spectroscopy under physiological conditions.The results show that this pyrano[4,3-b] pyran derivative observably quenches the fluorescence of BSA in a static quenching mode.The binding constants and the numbers of binding sites at different temperatures were obtained and the effects of some metal ions on the binding constant of the derivative and BSA were also discussed.According to the thermodynamic parameters,the main binding forces between them are hydrogen bonding and Van der Waals interactions.Furthermore,the binding distance and transfer efficiency of the interaction energy between BSA and the pyrano[4,3-b] pyran derivative were obtained according to the theory of Förster non-radiation energy transfer.The effect of this pyrano[4,3-b] pyran derivative on the conformation of BSA was analyzed via the synchronous fluorescence spectra and three-dimensional fluorescence spectra.
The mechanism of the interaction between bovine serum albumin(BSA) and pyrano[4,3-b] pyran derivative,2-amino-7-methyl-4-(4-nitrophenyl)-5-oxo-4,5-dihydropyrano[4,3-b] pyran-3-carbonitrile,was studied by means of fluorescence spectroscopy under physiological conditions.The results show that this pyrano[4,3-b] pyran derivative observably quenches the fluorescence of BSA in a static quenching mode.The binding constants and the numbers of binding sites at different temperatures were obtained and the effects of some metal ions on the binding constant of the derivative and BSA were also discussed.According to the thermodynamic parameters,the main binding forces between them are hydrogen bonding and Van der Waals interactions.Furthermore,the binding distance and transfer efficiency of the interaction energy between BSA and the pyrano[4,3-b] pyran derivative were obtained according to the theory of Förster non-radiation energy transfer.The effect of this pyrano[4,3-b] pyran derivative on the conformation of BSA was analyzed via the synchronous fluorescence spectra and three-dimensional fluorescence spectra.
2010, 27(5): 606-610
doi: 10.3724/SP.J.1095.2010.90375
Abstract:
A surface desorption atomospheric pressure chemical ionization mass spectrometry(SDAPCI-MS) method was employed to directly fingerprint 3 condiment vegetables including leek,onion,garlic with neither sample pre-treatment nor toxic chemical contamination.Identification of the molecular structure of desired ions was demonstrated by tandem mass spectrometry(MS/MS).The results show that the main components in chemical fingerprint spectrum of leek are 2-methyl-2-pentenal,methyl methanethiosulfinate,methyl allylthiosulfinate etc.,among which both methyl methanethiosulfinate and methyl allylthiosulfinate give a relatively strong signal of M+H2O·+. Intact onion bulb shows so few signals in the mass spectrum that only initial ions caused by corona discharge,such as H3O+(OH),and O2+,are detected.On the other hand,dissected onion bulb gives contrastively increased mass spectrum signals,namely,S-propentyl sulphinate,propyl allylthiosulfinate and propyl propylthiosulfinate.While allyl allylthiosulfinate is detected as the main volatiles of intact garlic bulb,dissected garlic bulb mainly gives S-propentyl sulphinate.Some other signals of interested,such as methyl methanethiosulfinate,methyl allylthiosulfinate from leek,S-propentyl sulphinate from onion and allyl allylthiosulfinate from garlic were structurally identified by tandem mass spectrometry(MS/MS).As the experimental findings shows,SDAPCI-MS technique is qualified for rapid non invasive analysis without sample manipulation prior to experiment,and provides practical and potential application in non-destructive testing and quality control for food.
A surface desorption atomospheric pressure chemical ionization mass spectrometry(SDAPCI-MS) method was employed to directly fingerprint 3 condiment vegetables including leek,onion,garlic with neither sample pre-treatment nor toxic chemical contamination.Identification of the molecular structure of desired ions was demonstrated by tandem mass spectrometry(MS/MS).The results show that the main components in chemical fingerprint spectrum of leek are 2-methyl-2-pentenal,methyl methanethiosulfinate,methyl allylthiosulfinate etc.,among which both methyl methanethiosulfinate and methyl allylthiosulfinate give a relatively strong signal of M+H2O·+. Intact onion bulb shows so few signals in the mass spectrum that only initial ions caused by corona discharge,such as H3O+(OH),and O2+,are detected.On the other hand,dissected onion bulb gives contrastively increased mass spectrum signals,namely,S-propentyl sulphinate,propyl allylthiosulfinate and propyl propylthiosulfinate.While allyl allylthiosulfinate is detected as the main volatiles of intact garlic bulb,dissected garlic bulb mainly gives S-propentyl sulphinate.Some other signals of interested,such as methyl methanethiosulfinate,methyl allylthiosulfinate from leek,S-propentyl sulphinate from onion and allyl allylthiosulfinate from garlic were structurally identified by tandem mass spectrometry(MS/MS).As the experimental findings shows,SDAPCI-MS technique is qualified for rapid non invasive analysis without sample manipulation prior to experiment,and provides practical and potential application in non-destructive testing and quality control for food.
2010, 27(5): 611-614
doi: 10.3724/SP.J.1095.2010.90397
Abstract:
A fluorescent method for the synchronous determination of 1-naphylamine and 2-naphylamine was developed.In order to avoid the interference from the two isomers,the synchronous fluorescence and first-order-derivative synchronous fluorescence spectra of the two isomers of naphylamine were studied,and the zero-crossing method for reading spectral intensities was adopted.At pH=7.8(phosphate buffered water solution) and △λ=120 nm,the synchronous fluorescence peaks were at 323 nm and 290 nm for 1-napylamine and 2-naphylamine,respectively.The first order derivative synchronous fluorescence intensities varied linearly with 1-naphylamine and 2-naphylamine concentrations in a range of 4.0×10-7~2.0×10-5 mol/L.The relative standard deviations(RSDs) of them were all below 5%.The limits of detection were 4.0×10-8 and 2.9×10-8 mol/L for 1-naphylamine and 2-naphylamine,respectively.The method was applied to the simultaneous determination of the two naphylamine isomers with satisfactory results.
A fluorescent method for the synchronous determination of 1-naphylamine and 2-naphylamine was developed.In order to avoid the interference from the two isomers,the synchronous fluorescence and first-order-derivative synchronous fluorescence spectra of the two isomers of naphylamine were studied,and the zero-crossing method for reading spectral intensities was adopted.At pH=7.8(phosphate buffered water solution) and △λ=120 nm,the synchronous fluorescence peaks were at 323 nm and 290 nm for 1-napylamine and 2-naphylamine,respectively.The first order derivative synchronous fluorescence intensities varied linearly with 1-naphylamine and 2-naphylamine concentrations in a range of 4.0×10-7~2.0×10-5 mol/L.The relative standard deviations(RSDs) of them were all below 5%.The limits of detection were 4.0×10-8 and 2.9×10-8 mol/L for 1-naphylamine and 2-naphylamine,respectively.The method was applied to the simultaneous determination of the two naphylamine isomers with satisfactory results.
2010, 27(5): 615-617
doi: 10.3724/SP.J.1095.2010.90429
Abstract:
Dehydroepiandrosterone(1) was oxidized with pyridinium chlorochromate(PCC) to obtain androst-4-en-3,6,17-trione(2),which was then submitted to reduction with NaBH4 in the presence of Co2+ to obtain 3β-hydroxyandrost-4-en-6,17-dione(3),a non-androgenic aromatase inhibitor.Compared with literature's methods,this method shortens the reaction steps and improves the reaction yield.The structure of compound 3 was characterized by NMR and IR.
Dehydroepiandrosterone(1) was oxidized with pyridinium chlorochromate(PCC) to obtain androst-4-en-3,6,17-trione(2),which was then submitted to reduction with NaBH4 in the presence of Co2+ to obtain 3β-hydroxyandrost-4-en-6,17-dione(3),a non-androgenic aromatase inhibitor.Compared with literature's methods,this method shortens the reaction steps and improves the reaction yield.The structure of compound 3 was characterized by NMR and IR.
2010, 27(5): 618-620
doi: 10.3724/SP.J.1095.2010.90527
Abstract:
4-Chlorophenyl isoferulate was synthesized in one-step from isoferulic acid and 4-chlorophenol without the protection of the hydroxyl of isoferulic acid in the presence of 4-dimethylpyridine(DMAP) as catalyst and dicyclohexylcarbodiimide(DCC) as dehydrating agent under ultrasonic irradiation at room temperature. When reactants were mixed in a n(isoferulic acid):n(4-chlorophenol):n(DCC):n(DMAP)=1:1.2:1.2:0.1, and exposed to ultrasonic irradiation for 2.5 h, the yield was 76.2%. The structure of the product was confirmed by elemental analysis, 1H NMR and IR. This method avoids the long reaction time and increases the yield compared with traditional synthetic method.
4-Chlorophenyl isoferulate was synthesized in one-step from isoferulic acid and 4-chlorophenol without the protection of the hydroxyl of isoferulic acid in the presence of 4-dimethylpyridine(DMAP) as catalyst and dicyclohexylcarbodiimide(DCC) as dehydrating agent under ultrasonic irradiation at room temperature. When reactants were mixed in a n(isoferulic acid):n(4-chlorophenol):n(DCC):n(DMAP)=1:1.2:1.2:0.1, and exposed to ultrasonic irradiation for 2.5 h, the yield was 76.2%. The structure of the product was confirmed by elemental analysis, 1H NMR and IR. This method avoids the long reaction time and increases the yield compared with traditional synthetic method.
