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2006 Volume 23 Issue 2
2006, 23(2): 117-121
Abstract:
The application of scanning probe microscopy(SPM) in intrinsically conducting polymer research is briefly reveiewed,including in morphology observation,nanofabrication,microcosmic electrical property measurements,electrochemistry research,in-situ measurement of film thickness change and so on.At the same time,some important variations of SPM and related techniques are briefly introduced. Finally,the future development trend of SPM in the study of intrinsically conducting polymers is described.
The application of scanning probe microscopy(SPM) in intrinsically conducting polymer research is briefly reveiewed,including in morphology observation,nanofabrication,microcosmic electrical property measurements,electrochemistry research,in-situ measurement of film thickness change and so on.At the same time,some important variations of SPM and related techniques are briefly introduced. Finally,the future development trend of SPM in the study of intrinsically conducting polymers is described.
2006, 23(2): 122-125
Abstract:
The breaking of the P(MMA/St/BPADA)/PS core-shell emulsion affected by electrolytes was studied.The relationship between the emulsion concentration and the transmittance and the curve of the transmittance vs the electrolyte concentration were obtained by means of spectrophotometry.Furthermore,the breaking process of the core-shell emulsion was found to divide into three stages:emulsion stabilization,aggregation due to incomplete breaking of the emulsion,and formation of flocculates by complete breaking of the emulsion.
The breaking of the P(MMA/St/BPADA)/PS core-shell emulsion affected by electrolytes was studied.The relationship between the emulsion concentration and the transmittance and the curve of the transmittance vs the electrolyte concentration were obtained by means of spectrophotometry.Furthermore,the breaking process of the core-shell emulsion was found to divide into three stages:emulsion stabilization,aggregation due to incomplete breaking of the emulsion,and formation of flocculates by complete breaking of the emulsion.
2006, 23(2): 126-130
Abstract:
Water-soluble chitosan was prepared by modification of chitosan with maleic anhydride,and then nylon 64 was grafted onto it by condensation polymerization.Products of different graft percentage and solubility were obtained by altering reagent feed ratio,and the optimum reagent feed ratio was determined to be n(MACS):n(hexamethylene diamine):n(butanedioic acid chloride)=1:10:7.5.The structure of the chitosan-graft-nylon was characterized by FTIR and 1H NMR.The preliminary results show that chitosan-graft-nylon can be used as a compatibilizer in the blends of chitosan and PA64.
Water-soluble chitosan was prepared by modification of chitosan with maleic anhydride,and then nylon 64 was grafted onto it by condensation polymerization.Products of different graft percentage and solubility were obtained by altering reagent feed ratio,and the optimum reagent feed ratio was determined to be n(MACS):n(hexamethylene diamine):n(butanedioic acid chloride)=1:10:7.5.The structure of the chitosan-graft-nylon was characterized by FTIR and 1H NMR.The preliminary results show that chitosan-graft-nylon can be used as a compatibilizer in the blends of chitosan and PA64.
2006, 23(2): 131-135
Abstract:
A series of Ni1-x-Cex-O(x=0.00~1.0) were prepared by the citrate method and characterized by means of XRD,H2-TPR technique and BET surface area measurement.It was found that the addition of CeO2 facilitated the reduction of NiO and increased the surface areas of the Ni1-x-Cex-O oxides,which correlated with the catalytic properties of the Ni1-x-Cex-O oxides for methane combustion.The catalytic activities of the Ni1-x-Cex-O oxides obviously increased with the increase of the Ce content and reached a maximum at x=0.3. A series of the Ni0.7-Ce0.3-O/ZrO2 catalysts were also prepared by the citrate method.The Ni0.7-Ce0.3-O/ZrO2 with a mass ratio=1:1 gave the highest catalytic activity,under the catalysis of which the temperature of methane complete oxidation into CO2 decreased from 530℃ to 480℃.
A series of Ni1-x-Cex-O(x=0.00~1.0) were prepared by the citrate method and characterized by means of XRD,H2-TPR technique and BET surface area measurement.It was found that the addition of CeO2 facilitated the reduction of NiO and increased the surface areas of the Ni1-x-Cex-O oxides,which correlated with the catalytic properties of the Ni1-x-Cex-O oxides for methane combustion.The catalytic activities of the Ni1-x-Cex-O oxides obviously increased with the increase of the Ce content and reached a maximum at x=0.3. A series of the Ni0.7-Ce0.3-O/ZrO2 catalysts were also prepared by the citrate method.The Ni0.7-Ce0.3-O/ZrO2 with a mass ratio=1:1 gave the highest catalytic activity,under the catalysis of which the temperature of methane complete oxidation into CO2 decreased from 530℃ to 480℃.
2006, 23(2): 136-139
Abstract:
A method based on capillary electrophoresis with high frequency conductivity detection was developed for the determination of captopril in body fluids.In this study,key factors for the separation and determination were studied and the best analysis conditions were obtained.In a buffer system of 3.0 mmol/L cyclohexylamine +5.0 mmol/L boric acid +0.50 mol/L ethanol,when 20.0 kV was used as the separation potential,the optimal separation was obtained.Under the chosen conditions,captopril was eluted within 8 min.
A method based on capillary electrophoresis with high frequency conductivity detection was developed for the determination of captopril in body fluids.In this study,key factors for the separation and determination were studied and the best analysis conditions were obtained.In a buffer system of 3.0 mmol/L cyclohexylamine +5.0 mmol/L boric acid +0.50 mol/L ethanol,when 20.0 kV was used as the separation potential,the optimal separation was obtained.Under the chosen conditions,captopril was eluted within 8 min.
2006, 23(2): 140-143
Abstract:
A novel triphenylamine-spirosilabifluorene alternating copolymer was synthesized by copolymerization of 2,2'-dibromo-9,9'-spiro-9-silabifluorene and triphenylamine diboronic acid via a palladium-catalyzed Suzuki coupling reaction.The dibromo monomer was synthesized in five steps starting from 1,2-dibromobenzene.Triphenylamine diboronic acid was obtained from triphenylamine in three steps.The structures of the monomers and the copolymer were verified by means of 1H NMR,MS,and FTIR.The molecular weight of the polymer was determined by gel permeation chromatography(GPC) analysis against polystyrene standards.The polymer has a Mn of 7 014,a Mw of 9 577,with a polydispersity of 1.36.The introduction of a spiro-structure leads to a high thermal stability(Tg=158.22℃) and a good solubility of the polymer in common organic solvents.The electrochemical behavior of the polymer was investigated with cyclic voltammetry.The reversible electrochemical oxidation and low ionization potential(-5.47eV,which is very close to the data reported for triphenylamine) suggest that the polymer might have potential application as a hole transport material for polymer LEDs.
A novel triphenylamine-spirosilabifluorene alternating copolymer was synthesized by copolymerization of 2,2'-dibromo-9,9'-spiro-9-silabifluorene and triphenylamine diboronic acid via a palladium-catalyzed Suzuki coupling reaction.The dibromo monomer was synthesized in five steps starting from 1,2-dibromobenzene.Triphenylamine diboronic acid was obtained from triphenylamine in three steps.The structures of the monomers and the copolymer were verified by means of 1H NMR,MS,and FTIR.The molecular weight of the polymer was determined by gel permeation chromatography(GPC) analysis against polystyrene standards.The polymer has a Mn of 7 014,a Mw of 9 577,with a polydispersity of 1.36.The introduction of a spiro-structure leads to a high thermal stability(Tg=158.22℃) and a good solubility of the polymer in common organic solvents.The electrochemical behavior of the polymer was investigated with cyclic voltammetry.The reversible electrochemical oxidation and low ionization potential(-5.47eV,which is very close to the data reported for triphenylamine) suggest that the polymer might have potential application as a hole transport material for polymer LEDs.
2006, 23(2): 144-148
Abstract:
According to characteristics of in-situ polymerization of monolithic column,the monolithic porous polymer which was thermally initiated within a glass micro-column was fabricated and applied to anion-exchange solid phase extraction(SPE).The effects of the amounts of the functional monomer,the initiator,the cross-linker,the porogenic solvent,the non-covalent monomer,and the temperature,the atmosphere,and the polymerization time for the reaction on the SPE micro-column properties were discussed.The proportion of all the components and reaction conditions were optimized respectively.The porous structure of the polymer was characterized by means of scanning electron microscopy(SEM).The absorption characteristic of the SPE monolithic micro-column was proved by ultra-violet absorption of NO2- at 214 nm.The experimental results show that the home-made anion exchange micro SPE column is of good absorption effect.Absorption efficiency of the micro SPE column could reach 72.4% with off-line sample treatment,and enrichment efficiency could reach 77.9 times with on-line sample treatment.
According to characteristics of in-situ polymerization of monolithic column,the monolithic porous polymer which was thermally initiated within a glass micro-column was fabricated and applied to anion-exchange solid phase extraction(SPE).The effects of the amounts of the functional monomer,the initiator,the cross-linker,the porogenic solvent,the non-covalent monomer,and the temperature,the atmosphere,and the polymerization time for the reaction on the SPE micro-column properties were discussed.The proportion of all the components and reaction conditions were optimized respectively.The porous structure of the polymer was characterized by means of scanning electron microscopy(SEM).The absorption characteristic of the SPE monolithic micro-column was proved by ultra-violet absorption of NO2- at 214 nm.The experimental results show that the home-made anion exchange micro SPE column is of good absorption effect.Absorption efficiency of the micro SPE column could reach 72.4% with off-line sample treatment,and enrichment efficiency could reach 77.9 times with on-line sample treatment.
2006, 23(2): 149-152
Abstract:
Experiments were conducted in an O/W microemulsified acid system with a wide salinity tolerance range(0~120 g/L).For comparison,the chemical reactions of the N80 steel and the sand particles in two acid systems,including mud acid and microemulsified acid,were studied.The different characteristics of the chemical reactions in unconsolidated sand packs of the two acid systems were observed as well as their acidizing effects in cores.After microemulsification of the mud acid,its corrosion rates to the N80 steel and the sand particles were found to decrease by 45% and 40% respectively compared with that of mud acid,and lower loss rates in unconsolidated sand packs were observed.In an unconsolidated sand pack with a length of 50 cm,when injected at a rate of 0.5 mL/min for 60 min,the mud acid reacted at the distance of 0~20 cm,and the microemulsified acid at the 13~50 cm.In core flooding,the end face near the outlet became loose with microemulsified acid;however,the inlet end face became loose with mud acid.Because of the excellent corrosion inhibition performance after emulsification,the microemulsified mud acid system can flow to reservoir' deep parts and be reliably applied to indepth reservoir acidizing.
Experiments were conducted in an O/W microemulsified acid system with a wide salinity tolerance range(0~120 g/L).For comparison,the chemical reactions of the N80 steel and the sand particles in two acid systems,including mud acid and microemulsified acid,were studied.The different characteristics of the chemical reactions in unconsolidated sand packs of the two acid systems were observed as well as their acidizing effects in cores.After microemulsification of the mud acid,its corrosion rates to the N80 steel and the sand particles were found to decrease by 45% and 40% respectively compared with that of mud acid,and lower loss rates in unconsolidated sand packs were observed.In an unconsolidated sand pack with a length of 50 cm,when injected at a rate of 0.5 mL/min for 60 min,the mud acid reacted at the distance of 0~20 cm,and the microemulsified acid at the 13~50 cm.In core flooding,the end face near the outlet became loose with microemulsified acid;however,the inlet end face became loose with mud acid.Because of the excellent corrosion inhibition performance after emulsification,the microemulsified mud acid system can flow to reservoir' deep parts and be reliably applied to indepth reservoir acidizing.
2006, 23(2): 153-156
Abstract:
The UV spectra,photo-degradation kinetics,and photostability of four axially alkoxy substituted naphthalocyanine silicon compounds(Sinc(OR)2,R=CH3),C2H5,C3H7 and C4H9) were investigated in DMSO,DMF and CH2Cl2,respectively.The results indicate that the maximal absorption bands of the compounds increase with increased carbon number of the axially alkoxy substituted groups in the same solvent.Moreover,the photostability also gradually increase with increased carbon number of the axially alkoxy substituted groups in DMSO and CH2Cl2.The photostability order for the same Sinc(OR)2 compound in different solvent is:DMSO >CH2Cl2 >DMF.
The UV spectra,photo-degradation kinetics,and photostability of four axially alkoxy substituted naphthalocyanine silicon compounds(Sinc(OR)2,R=CH3),C2H5,C3H7 and C4H9) were investigated in DMSO,DMF and CH2Cl2,respectively.The results indicate that the maximal absorption bands of the compounds increase with increased carbon number of the axially alkoxy substituted groups in the same solvent.Moreover,the photostability also gradually increase with increased carbon number of the axially alkoxy substituted groups in DMSO and CH2Cl2.The photostability order for the same Sinc(OR)2 compound in different solvent is:DMSO >CH2Cl2 >DMF.
2006, 23(2): 157-160
Abstract:
The interaction mechanism between microperoxidase-11 and Yb3+ was studied by means of UV-Vis absorption spectroscopic technique.It was found that Yb3+ could bond with the carbonyl oxygen of the metacetonic acid group in the heme group of the MP-11 molecule.One Yb3+ ion links with one carbonyl oxygen of the metacetonic acid group.This kind of interaction results in the increase in the non-planarity of the porphyrin group in the heme group and the decrease in the energy for the π-π* transition.However,the probability of the π-π* transition is decreased.Yb3+ could not link with the carbonyl oxygen of the amido group in the peptide of the MP-11 molecule because the carbonyl oxygen of the amido group in the peptide is embedded in the hydrophobic environment in the peptide.
The interaction mechanism between microperoxidase-11 and Yb3+ was studied by means of UV-Vis absorption spectroscopic technique.It was found that Yb3+ could bond with the carbonyl oxygen of the metacetonic acid group in the heme group of the MP-11 molecule.One Yb3+ ion links with one carbonyl oxygen of the metacetonic acid group.This kind of interaction results in the increase in the non-planarity of the porphyrin group in the heme group and the decrease in the energy for the π-π* transition.However,the probability of the π-π* transition is decreased.Yb3+ could not link with the carbonyl oxygen of the amido group in the peptide of the MP-11 molecule because the carbonyl oxygen of the amido group in the peptide is embedded in the hydrophobic environment in the peptide.
2006, 23(2): 161-164
Abstract:
Oxidation of oleic acid with ozone is an important way to produce azelaic acid.The process contains a two-step reaction,ozonization and further oxidation by oxygen in the presence of a catalyst.A mixed solvent system was used for the first step and a series of new catalysts were respectively introduced into the second step.The activity of each catalyst was studied by determining the concentration of active oxygen(CAO) in the reaction and the selectivity was investigated by comparing the corresponding yield of azelaic acid.The results show that the reactivity order of the catalysts studied is V2O5 >MnO2 >MoO3 >PbO2 >Co(OAc)2·4H2O >Mn(OAc)2·4H2O,and the selectivity order is MoO3 >PbO2 >MnO2 >Co(OAc)2·4H2O >Mn(OAc)2·4H2O >V2O5.With MoO3 or PbO2 as the catalyst,the yield of azelaic acid can be maintained above 75%.
Oxidation of oleic acid with ozone is an important way to produce azelaic acid.The process contains a two-step reaction,ozonization and further oxidation by oxygen in the presence of a catalyst.A mixed solvent system was used for the first step and a series of new catalysts were respectively introduced into the second step.The activity of each catalyst was studied by determining the concentration of active oxygen(CAO) in the reaction and the selectivity was investigated by comparing the corresponding yield of azelaic acid.The results show that the reactivity order of the catalysts studied is V2O5 >MnO2 >MoO3 >PbO2 >Co(OAc)2·4H2O >Mn(OAc)2·4H2O,and the selectivity order is MoO3 >PbO2 >MnO2 >Co(OAc)2·4H2O >Mn(OAc)2·4H2O >V2O5.With MoO3 or PbO2 as the catalyst,the yield of azelaic acid can be maintained above 75%.
2006, 23(2): 165-168
Abstract:
With water as solvent,the bis-phenol ester of spirocylic pentaerythritol bischlorophosphatidic acid was prepared from spirocyclic pentaerythritol bis-chlorophosphatide and phenol under alkaline condition.The reaction time was determined by monitering the reaction process with the absorbency variation of phenol sodium in the reaction system at 269.6 nm.The product structure was characterized with FTIR,1H NMR and the phosphorus amount.The thermal stability of the product was analysed with TG measurement.
With water as solvent,the bis-phenol ester of spirocylic pentaerythritol bischlorophosphatidic acid was prepared from spirocyclic pentaerythritol bis-chlorophosphatide and phenol under alkaline condition.The reaction time was determined by monitering the reaction process with the absorbency variation of phenol sodium in the reaction system at 269.6 nm.The product structure was characterized with FTIR,1H NMR and the phosphorus amount.The thermal stability of the product was analysed with TG measurement.
2006, 23(2): 169-172
Abstract:
Grafting of glycidyl methylacrylate(GMA) on chlorinated polypropylene(CPP) by melt grafting process was carried out with benzoperoxide(BPO) as the initiator,and the structure of the purified product was characterized by FTIR.Effects of reaction temperature,amount of BPO and monomer on the adhesion properties of the modified CPP were studied.The optimized reaction conditions are:reaction temperature 140℃,ω(BPO)=0.4%,ω(GMA)>6%,and n(St)/n(GMA)=1.4.The experimental results show that the chlorinated polypropylene has a better adhesion property for aluminum and the value of peel strength reaches 2 449.92 N/m.
Grafting of glycidyl methylacrylate(GMA) on chlorinated polypropylene(CPP) by melt grafting process was carried out with benzoperoxide(BPO) as the initiator,and the structure of the purified product was characterized by FTIR.Effects of reaction temperature,amount of BPO and monomer on the adhesion properties of the modified CPP were studied.The optimized reaction conditions are:reaction temperature 140℃,ω(BPO)=0.4%,ω(GMA)>6%,and n(St)/n(GMA)=1.4.The experimental results show that the chlorinated polypropylene has a better adhesion property for aluminum and the value of peel strength reaches 2 449.92 N/m.
2006, 23(2): 173-178
Abstract:
Six bicadmium(Ⅱ) cryptates[Cd2Ln] were synthesized by the[2+3] Schiff base condensation of 2-aminoethyl-bi(3-aminopropyl) amine with sodium 2,6-diformyl-4-R-phenolate(R=CH3,CH3O,(C(CH3)3,F,Cl,Br,n=1,2,3,4,5,6,respectively) in the presence of Cd2+.After one imine group of[Cd2L1] was hydrolyzed and solvent addition,with no ring opening,cryptate[Cd2Lh] was produced.The structures of the seven complexes were confirmed by elemental analysis,IR,electronic spectrum,and ES-MS.The toxicities of the complexes were evaluated by testing antimicrobial activity against bacterial strains.The complexes were active against four organisms tested with no exception,showing highest antimicrobial activity against staphyloccus aureus.
Six bicadmium(Ⅱ) cryptates[Cd2Ln] were synthesized by the[2+3] Schiff base condensation of 2-aminoethyl-bi(3-aminopropyl) amine with sodium 2,6-diformyl-4-R-phenolate(R=CH3,CH3O,(C(CH3)3,F,Cl,Br,n=1,2,3,4,5,6,respectively) in the presence of Cd2+.After one imine group of[Cd2L1] was hydrolyzed and solvent addition,with no ring opening,cryptate[Cd2Lh] was produced.The structures of the seven complexes were confirmed by elemental analysis,IR,electronic spectrum,and ES-MS.The toxicities of the complexes were evaluated by testing antimicrobial activity against bacterial strains.The complexes were active against four organisms tested with no exception,showing highest antimicrobial activity against staphyloccus aureus.
2006, 23(2): 179-183
Abstract:
Lithium polyacrylate(PAA-Li) prepared in our lab was used as the carbon source and part of the lithium source to synthesize LiFePO4/C.The sample AA75625 synthesized from 75%(molar fraction) PAA-Li and 25% LiOH·H2O displayed a discharge capacity of 161 mA·h/g at the 10th cycle at a current density of 0.04×10-3 A/cm2 and 20℃,showing good cycling performance.It was proved by XRD that the main crystalline phase of all the samples was LiFePO4.Impurity was found in the samples calcinated at 550℃ or lower,and some peaks attributed to Fe3O4 were found for the sample synthesized by 100% LiOH·H2O at 500℃.The X-ray energy spectrum was used to detect the value of Fe:P(molar ratio) at different randomly chosen areas of the sample AA75625.It was discovered that the molar ratio of Fe to P was inhomogeneous and the average value was 2.2,while the significance interval was(1.3,3.1);therefore,it deviated from(1:1) significantly,which meant that Fe and P distributed inhomogeneously on the surface of the particles.The probable reason causing the inhomogeneous molar ratio of Fe to P was discussed,and it was pointed out that the phenomenon caused the capacity loss.
Lithium polyacrylate(PAA-Li) prepared in our lab was used as the carbon source and part of the lithium source to synthesize LiFePO4/C.The sample AA75625 synthesized from 75%(molar fraction) PAA-Li and 25% LiOH·H2O displayed a discharge capacity of 161 mA·h/g at the 10th cycle at a current density of 0.04×10-3 A/cm2 and 20℃,showing good cycling performance.It was proved by XRD that the main crystalline phase of all the samples was LiFePO4.Impurity was found in the samples calcinated at 550℃ or lower,and some peaks attributed to Fe3O4 were found for the sample synthesized by 100% LiOH·H2O at 500℃.The X-ray energy spectrum was used to detect the value of Fe:P(molar ratio) at different randomly chosen areas of the sample AA75625.It was discovered that the molar ratio of Fe to P was inhomogeneous and the average value was 2.2,while the significance interval was(1.3,3.1);therefore,it deviated from(1:1) significantly,which meant that Fe and P distributed inhomogeneously on the surface of the particles.The probable reason causing the inhomogeneous molar ratio of Fe to P was discussed,and it was pointed out that the phenomenon caused the capacity loss.
2006, 23(2): 184-187
Abstract:
This paper reports the antibacterial property of quaternary copolymer of 4-vinyl pyridine and acrylamide (Quaternary P(4VP-co-AM),QCVA) against Escherichia Coli,the influence of pH value on the antibacterial property of QCVA with the method of plate counting live bacterium,and the antibacterial mechanism of QCVA by measuring the activities of β-D-galactosidase and TTC-DHE.The experimental results indicate that cationic polyacrylamide of quaternary pyridine salt-type possesses excellent antibacterial property.In addition in a certain pH range,the greater the pH value,the better the antibacterial effect of QCVA.The measured results of the activities of β-D-galactosidase and TTC-DHE show that the antibacterial effect of QCVA is mainly based on sterilization action besides restraining action.
This paper reports the antibacterial property of quaternary copolymer of 4-vinyl pyridine and acrylamide (Quaternary P(4VP-co-AM),QCVA) against Escherichia Coli,the influence of pH value on the antibacterial property of QCVA with the method of plate counting live bacterium,and the antibacterial mechanism of QCVA by measuring the activities of β-D-galactosidase and TTC-DHE.The experimental results indicate that cationic polyacrylamide of quaternary pyridine salt-type possesses excellent antibacterial property.In addition in a certain pH range,the greater the pH value,the better the antibacterial effect of QCVA.The measured results of the activities of β-D-galactosidase and TTC-DHE show that the antibacterial effect of QCVA is mainly based on sterilization action besides restraining action.
2006, 23(2): 188-192
Abstract:
Lipase was immobilized in sodium bis(2-ethylhexyl) sulphosuccinate(AOT)-n-heptane microemulsion as a matrix with gelatin,and its catalytic activity in an organic medium for the hydrolysis of glycerol α-monostearate was studied.Results indicate that the concentrations of gelatin and AOT,the R value(the molar ratio of water to AOT) have effects on the catalytic activity of lipase.The lipase immobilization was optimized when the AOT microemulsion composed of 75% n-heptane,9% buffer and 16% AOT(mass fraction),and the composition of gelatin was 17%,and the R value 72.Kinetic studies showed that when its concentration was constant,lipase in the gel exerted its maximum catalytic activity as the concentration of the substrate reached 0.10 mol/L.The reaction reached its balance after 15 h reaction time.
Lipase was immobilized in sodium bis(2-ethylhexyl) sulphosuccinate(AOT)-n-heptane microemulsion as a matrix with gelatin,and its catalytic activity in an organic medium for the hydrolysis of glycerol α-monostearate was studied.Results indicate that the concentrations of gelatin and AOT,the R value(the molar ratio of water to AOT) have effects on the catalytic activity of lipase.The lipase immobilization was optimized when the AOT microemulsion composed of 75% n-heptane,9% buffer and 16% AOT(mass fraction),and the composition of gelatin was 17%,and the R value 72.Kinetic studies showed that when its concentration was constant,lipase in the gel exerted its maximum catalytic activity as the concentration of the substrate reached 0.10 mol/L.The reaction reached its balance after 15 h reaction time.
2006, 23(2): 193-197
Abstract:
The synthesis of aminofluorescein,an important fluorescein probe,was studied systematically.A nitrofluorescein compound was obtained from 4-nitrophthalic acid and resoreinol in the presence of zinc chloride by melting reaction with a yield of 85.0%.Reduction of the nitrofluorescein compound with Na2S/NaHS,Na2S2,SnCl2,or H2/Raney nickel yielded aminofluorescein compounds.5-Aminofluorescein and 6-aminofluorescein were isolated by recrystallization of the obtained mixture in 6% hydrochloric acid with 39.6% and 14.5% yields respectively.The fluorescence intensity of the product,λEX and λEM,were determined with a fluorometer.The purities of the products were identified with HPLC,and the structures of the products were charac-terized by 1H NMR,13C NMR,IR and MS.
The synthesis of aminofluorescein,an important fluorescein probe,was studied systematically.A nitrofluorescein compound was obtained from 4-nitrophthalic acid and resoreinol in the presence of zinc chloride by melting reaction with a yield of 85.0%.Reduction of the nitrofluorescein compound with Na2S/NaHS,Na2S2,SnCl2,or H2/Raney nickel yielded aminofluorescein compounds.5-Aminofluorescein and 6-aminofluorescein were isolated by recrystallization of the obtained mixture in 6% hydrochloric acid with 39.6% and 14.5% yields respectively.The fluorescence intensity of the product,λEX and λEM,were determined with a fluorometer.The purities of the products were identified with HPLC,and the structures of the products were charac-terized by 1H NMR,13C NMR,IR and MS.
2006, 23(2): 198-202
Abstract:
A hydroxyl-terminal fluorine-containing macromonomer of about 6 000 molecule weight was synthesized by radical copolymerization of dodecafluroheptyl acrylate with other vinyl monomers in the presence of mercaptoethanol as chain-transfer agent.A tri-block co-polymer was obtained by reacting the macromonomer with NCO-terminal prepolymer with build-in hydrophilic groups.An aqueous block co-polymer dispersion was prepared by dispersing the tri-block co-polymer in water.The TEM photograph shows that the dispersion particles have a core-shell structure,and the fluorine-containing polyacrylate forms micro domains in the continuous polyurethane phase;ART,XPS and contact angle studies show that the fluorine groups are enriched in the film surface.
A hydroxyl-terminal fluorine-containing macromonomer of about 6 000 molecule weight was synthesized by radical copolymerization of dodecafluroheptyl acrylate with other vinyl monomers in the presence of mercaptoethanol as chain-transfer agent.A tri-block co-polymer was obtained by reacting the macromonomer with NCO-terminal prepolymer with build-in hydrophilic groups.An aqueous block co-polymer dispersion was prepared by dispersing the tri-block co-polymer in water.The TEM photograph shows that the dispersion particles have a core-shell structure,and the fluorine-containing polyacrylate forms micro domains in the continuous polyurethane phase;ART,XPS and contact angle studies show that the fluorine groups are enriched in the film surface.
2006, 23(2): 203-206
Abstract:
Rich and inexpensive fats and oils from animals and plants,which are readily available in China,have not found effective utilization.In order to make better use of these resources,lipase-catalyzed acidolysis of lard with caprylic acid to produce functional lipids was investigated.It was found that among the five lipases that were tested in the initial screening,immobilized lipase TL IM from T.languginosa was the best catalyst for the incorporation of caprylic acid into lard.The effects of enzyme loading,organic solvent,substrate ratio, reaction time,and temperature on the acidolysis reaction were further studied by HPLC analysis of the products.The results showed that the highest caprylic acid incorporation ratio,(34.9±1.7)%,was obtained in hexane at 15% of enzyme loading,1:2 molar ratio of lard to caprylic acid and 55℃ for 24 h,and a caprylic acid incorpration ratio of (32.4±2.6)% at 20% of enzyme loading,1:2 molar ratio of lard to caprylic acid and 50℃ for 24 h in no solvent system was obtained.
Rich and inexpensive fats and oils from animals and plants,which are readily available in China,have not found effective utilization.In order to make better use of these resources,lipase-catalyzed acidolysis of lard with caprylic acid to produce functional lipids was investigated.It was found that among the five lipases that were tested in the initial screening,immobilized lipase TL IM from T.languginosa was the best catalyst for the incorporation of caprylic acid into lard.The effects of enzyme loading,organic solvent,substrate ratio, reaction time,and temperature on the acidolysis reaction were further studied by HPLC analysis of the products.The results showed that the highest caprylic acid incorporation ratio,(34.9±1.7)%,was obtained in hexane at 15% of enzyme loading,1:2 molar ratio of lard to caprylic acid and 55℃ for 24 h,and a caprylic acid incorpration ratio of (32.4±2.6)% at 20% of enzyme loading,1:2 molar ratio of lard to caprylic acid and 50℃ for 24 h in no solvent system was obtained.
2006, 23(2): 207-211
Abstract:
Magnetic fluorouracil-loaded chitosan microspheres were prepared by an emulsion chemical-crosslinking method.The Fe content was determined by titration with K2Cr2O7.The magnetic susceptibility was measured by means of a magnetic balance,and the morphologies of the magnetic microspheres were observed under a scanning electron microscope.The results demonstrate that the magnetic fluorouracil-loaded chitosan microspheres exhibited strong paramagnetism with 4.55%~11.44%(mass fraction) of Fe3O4,1.86%~9.42%(mass fraction) of FU,39.48%~85.30% of which encapsulated,and the diameters were in the range of 1~10 μm.The drug releasing property was studied in the phosphate buffer(pH=7.4) solution,and the results show that FU could be released slowly from the microspheres with a longer release period;the content of Fe3O4 has an unconspicuous effect on drug release,and drug release was controlled by diffusion mechanism,and the drug releasing from the microspheres became faster with the increase of the drug content.The magnetic fluorouracil-loaded chitosan microspheres are a potential candidate as magnetic-targeting system for drug-controlled release.
Magnetic fluorouracil-loaded chitosan microspheres were prepared by an emulsion chemical-crosslinking method.The Fe content was determined by titration with K2Cr2O7.The magnetic susceptibility was measured by means of a magnetic balance,and the morphologies of the magnetic microspheres were observed under a scanning electron microscope.The results demonstrate that the magnetic fluorouracil-loaded chitosan microspheres exhibited strong paramagnetism with 4.55%~11.44%(mass fraction) of Fe3O4,1.86%~9.42%(mass fraction) of FU,39.48%~85.30% of which encapsulated,and the diameters were in the range of 1~10 μm.The drug releasing property was studied in the phosphate buffer(pH=7.4) solution,and the results show that FU could be released slowly from the microspheres with a longer release period;the content of Fe3O4 has an unconspicuous effect on drug release,and drug release was controlled by diffusion mechanism,and the drug releasing from the microspheres became faster with the increase of the drug content.The magnetic fluorouracil-loaded chitosan microspheres are a potential candidate as magnetic-targeting system for drug-controlled release.
2006, 23(2): 212-214
Abstract:
The rare earth(Ⅲ) perfluorooctanesulfonates(RE(OSO2C8F17)3,RE:Sc,Y,La~Lu) catalysts have been prepared and used in Friedel-Crafts alkylation in fluorous biphasic systems.Perfluorohexane(C6F14),perfluoromethylcyclohexane(C7F14),perfluorotoluen(C7F8),perfluorooctane(C8F18),perfluorooctyl bromide(C8F17Br) and perfluorodecalin(C10F18,cis and trans-mixture) can be used as the fluorous solvent for this kind of reaction.The catalytic activities of other rare earth metal salts with different ligands were tested.The results show that Yb(OSO2C8F17)3 and(C10F18) were the best catalyst and fluorous solvent respec-tively.The yield of alkylation of anisole with benzyl alcohol was 96% in the presence of Yb(OSO2C8F17)3 and C10F18.By simple phase-separation the fluorous phase containing only catalyst could be re-utilized up to five times with a slight decrease in activity.
The rare earth(Ⅲ) perfluorooctanesulfonates(RE(OSO2C8F17)3,RE:Sc,Y,La~Lu) catalysts have been prepared and used in Friedel-Crafts alkylation in fluorous biphasic systems.Perfluorohexane(C6F14),perfluoromethylcyclohexane(C7F14),perfluorotoluen(C7F8),perfluorooctane(C8F18),perfluorooctyl bromide(C8F17Br) and perfluorodecalin(C10F18,cis and trans-mixture) can be used as the fluorous solvent for this kind of reaction.The catalytic activities of other rare earth metal salts with different ligands were tested.The results show that Yb(OSO2C8F17)3 and(C10F18) were the best catalyst and fluorous solvent respec-tively.The yield of alkylation of anisole with benzyl alcohol was 96% in the presence of Yb(OSO2C8F17)3 and C10F18.By simple phase-separation the fluorous phase containing only catalyst could be re-utilized up to five times with a slight decrease in activity.
2006, 23(2): 215-217
Abstract:
Ten new acylthiourea derivatives with fnroyl and 5-aryl-1,3,4-oxadiazol-2-amino-yl were prepared.Their structures were confirmed by IR,1H NMR and elemental analysis.The biological test results show that most of these compounds have good fungicidal activity.To Botrytis cinereapers,fungicidal activity of some of the compounds can reach 97%.
Ten new acylthiourea derivatives with fnroyl and 5-aryl-1,3,4-oxadiazol-2-amino-yl were prepared.Their structures were confirmed by IR,1H NMR and elemental analysis.The biological test results show that most of these compounds have good fungicidal activity.To Botrytis cinereapers,fungicidal activity of some of the compounds can reach 97%.
2006, 23(2): 218-220
Abstract:
The title complex {AgLNO3}n(L=1,4-bis(3,4-dimethoxylphenylthio)butane) was synthesized and characterized by X-ray diffraction analysis.The Ag(Ⅰ) center is three-coordinated in a distorted pyramidal geometry.Dithioether ligand is often used as a bridging ligand in the construction of a one-dimensional structure.The complex molecules form a grid shape quasi-two-dimensional structure through neighboring O…(Ag) interactions.
The title complex {AgLNO3}n(L=1,4-bis(3,4-dimethoxylphenylthio)butane) was synthesized and characterized by X-ray diffraction analysis.The Ag(Ⅰ) center is three-coordinated in a distorted pyramidal geometry.Dithioether ligand is often used as a bridging ligand in the construction of a one-dimensional structure.The complex molecules form a grid shape quasi-two-dimensional structure through neighboring O…(Ag) interactions.
2006, 23(2): 221-223
Abstract:
In a toluene/water heterogeneous system,4-methylphenyl allyl ether(Ⅰ) was obtained from the reaction between 4-methylphenol and allyl bromide with a high yield at 70℃ for 24 h in the presence of a phase transfer catalyst trioctadecyl methyl ammonium chloride and excess sodium hydroxide.Compound(Ⅰ) was converted into compound(Ⅳ) after Claisen rearrangement,etherification and Claisen rearrangement again.When the reaction lasted for 72 h, compounds(Ⅰ),(Ⅱ) and(Ⅲ) were obtained with the yields of 29%,50%,and 10%,respectively under the above reaction conditions.Compound(Ⅳ) was obtained from compound(Ⅲ) via Claisen rearrangement.
In a toluene/water heterogeneous system,4-methylphenyl allyl ether(Ⅰ) was obtained from the reaction between 4-methylphenol and allyl bromide with a high yield at 70℃ for 24 h in the presence of a phase transfer catalyst trioctadecyl methyl ammonium chloride and excess sodium hydroxide.Compound(Ⅰ) was converted into compound(Ⅳ) after Claisen rearrangement,etherification and Claisen rearrangement again.When the reaction lasted for 72 h, compounds(Ⅰ),(Ⅱ) and(Ⅲ) were obtained with the yields of 29%,50%,and 10%,respectively under the above reaction conditions.Compound(Ⅳ) was obtained from compound(Ⅲ) via Claisen rearrangement.
2006, 23(2): 224-226
Abstract:
The synthesis of 4-ethoxycarbonyl-3-methyl-5-[α-(p-nitrophenoxy) myristyl]hydrazide-1H-pyrazole(Ⅲ) is reported.4-Ethoxycarbonyl-5-hydrazino-3-methyl pyrazole(Ⅰ) was prepared by the reaction of thiocarbohydrazide with acetylacetic ether,and the reaction of compound Ⅰ and α-(P-nitrophenoxy) myristyl chloride gave compound Ⅲ(yield 66.7%).The structure of compound Ⅲ was characterized by elemental analysis,IR and 1H NMR
The synthesis of 4-ethoxycarbonyl-3-methyl-5-[α-(p-nitrophenoxy) myristyl]hydrazide-1H-pyrazole(Ⅲ) is reported.4-Ethoxycarbonyl-5-hydrazino-3-methyl pyrazole(Ⅰ) was prepared by the reaction of thiocarbohydrazide with acetylacetic ether,and the reaction of compound Ⅰ and α-(P-nitrophenoxy) myristyl chloride gave compound Ⅲ(yield 66.7%).The structure of compound Ⅲ was characterized by elemental analysis,IR and 1H NMR
2006, 23(2): 227-229
Abstract:
The non-isothermal decomposition kinetics of complexes of light rare earth bromides with alanine was studied using DSC technique.The kinetic parameters(activation energy E,pre-exponential factor A) were obtained from the analysis of the DSC curves by means of Ozawa method,Kissinger method,Achar method,and Coats-Redfern method respectively.The most probable mechanism functions were suggested by comparing the kinetic parameters.
The non-isothermal decomposition kinetics of complexes of light rare earth bromides with alanine was studied using DSC technique.The kinetic parameters(activation energy E,pre-exponential factor A) were obtained from the analysis of the DSC curves by means of Ozawa method,Kissinger method,Achar method,and Coats-Redfern method respectively.The most probable mechanism functions were suggested by comparing the kinetic parameters.
2006, 23(2): 230-232
Abstract:
Lead alkoxide complexes Pb(OEt)4,Pb(OBu)4,Pb(OCH2CH2OCH3)4,Pb(OEt)2(acac)2,Pb(OBu)2(acac)2 and Pb(OCH2CH2OCH3)2(acac)2 were directly synthesized by means of electrochemical dissolution of lead in a cell without any diaphragm. The products were characterized by FT-IR,Raman spectra and NMR.The experimental results show that selecting R4NBr as the conductive additive could improve product yields and prevent the lead anode from passivation.The data also show that a direct electrochemical preparation of lead complexes Pb(OCH2CH2OCH3)4,Pb(OEt)2(acac)2,Pb(OBu)2(acac)2 and Pb(OCH2CH2OCH3)2(acac)2 exhibits a high current efficiency and a high electrolysis yield.
Lead alkoxide complexes Pb(OEt)4,Pb(OBu)4,Pb(OCH2CH2OCH3)4,Pb(OEt)2(acac)2,Pb(OBu)2(acac)2 and Pb(OCH2CH2OCH3)2(acac)2 were directly synthesized by means of electrochemical dissolution of lead in a cell without any diaphragm. The products were characterized by FT-IR,Raman spectra and NMR.The experimental results show that selecting R4NBr as the conductive additive could improve product yields and prevent the lead anode from passivation.The data also show that a direct electrochemical preparation of lead complexes Pb(OCH2CH2OCH3)4,Pb(OEt)2(acac)2,Pb(OBu)2(acac)2 and Pb(OCH2CH2OCH3)2(acac)2 exhibits a high current efficiency and a high electrolysis yield.
