Login In
2009 Volume 26 Issue 3
2009, 26(3): 249-252
Abstract:
The separation of neutral macrocyclic calix[4]pyrroles with 1-butyl-3-methylimidazolium chloride as background electrolyte in acetonitrile was carried out by nonaqueous capillary electrophoresis.Hydrogen bonding effect plays an important role in the separation and is the prerequisite of the separation according to the direction of applied voltage and migration order of electoosmotic flow and the analytes.There is a CH-π effect in this separation according to Debye-Hükel theory.In order to investigate the mechanism of the separation,the molar fraction of three species(C4P,C4PCl-,C4PCl-R+) were calculated.It was found that the C4PCl- was the major component and decreased with the increase of BGE concentration,C4PCl-R+ increased with the increase of BGE concentration.
The separation of neutral macrocyclic calix[4]pyrroles with 1-butyl-3-methylimidazolium chloride as background electrolyte in acetonitrile was carried out by nonaqueous capillary electrophoresis.Hydrogen bonding effect plays an important role in the separation and is the prerequisite of the separation according to the direction of applied voltage and migration order of electoosmotic flow and the analytes.There is a CH-π effect in this separation according to Debye-Hükel theory.In order to investigate the mechanism of the separation,the molar fraction of three species(C4P,C4PCl-,C4PCl-R+) were calculated.It was found that the C4PCl- was the major component and decreased with the increase of BGE concentration,C4PCl-R+ increased with the increase of BGE concentration.
2009, 26(3): 253-256
Abstract:
A series of stable and effective 4-hydroxyphenyl-D-glucopyranoside derivates were synthesized.The 10 new compounds were characterized by 1H NMR and HRMS.The preliminary test of bioactivity showed that they displayed notable inhibitions to tyrosinase.The inhibitions of compounds 13,14,15,16 and 19 to tyrosinase were equal or better than that of natural arbutin.
A series of stable and effective 4-hydroxyphenyl-D-glucopyranoside derivates were synthesized.The 10 new compounds were characterized by 1H NMR and HRMS.The preliminary test of bioactivity showed that they displayed notable inhibitions to tyrosinase.The inhibitions of compounds 13,14,15,16 and 19 to tyrosinase were equal or better than that of natural arbutin.
2009, 26(3): 257-262
Abstract:
A novel phospholipase A2(PLA2) named GBB-PLA2 was purified and determined by SDS-PAGE and mass spectrometry,from the snake venom of Glyodius blomhoffi Brevicaudaus.Electrophoresis,mass spectrometry,ICP-AES,UV-Vis and fluorescence spectroscopy techniques were utilized for the systematic study of GBB-PLA2.The purified protein possessed molecular mass of 13 965.07 amu.Protein identification of GBB-PLA2 was carried out by HPLC-ESI-MS/MS analysis.Four homogeneous peptides and 1 peptide of two PLA2s Agkistrodon halys Pallas and Deinagkisrodon acutus snake venoms were identified from GBB-PLA2.The results from native Sephacryl S-300 gel filtration and MALDI-TOF mass spectrometry indicate that GBB-PLA2 exists as a stable monomeric molecule in aqueous solution.The experimental data from ICP-AES reveal that the purified GBB-PLA2 is a Ca2+ bound protein with a calcium stoichiometry of 1:1([Ca2+]/[GBB-PLA2]).Removal of Ca2+ from GBB-PLA2 decreases the hydrolysis activity of PLA2 by 90%,suggesting that Ca2+ ions play a critical role for GBB-PLA2.The addition of exogenous Ca2+ can accelerate the hydrolysis rate of the substrate DPPC for GBB-PLA2.Ca2+ increases the thermostability by 3 ℃ and changes the secondary structure of GBB-PLA2,indicating that the presence of Ca2+ helps to maintain the structure integrity of GBB-PLA2.
A novel phospholipase A2(PLA2) named GBB-PLA2 was purified and determined by SDS-PAGE and mass spectrometry,from the snake venom of Glyodius blomhoffi Brevicaudaus.Electrophoresis,mass spectrometry,ICP-AES,UV-Vis and fluorescence spectroscopy techniques were utilized for the systematic study of GBB-PLA2.The purified protein possessed molecular mass of 13 965.07 amu.Protein identification of GBB-PLA2 was carried out by HPLC-ESI-MS/MS analysis.Four homogeneous peptides and 1 peptide of two PLA2s Agkistrodon halys Pallas and Deinagkisrodon acutus snake venoms were identified from GBB-PLA2.The results from native Sephacryl S-300 gel filtration and MALDI-TOF mass spectrometry indicate that GBB-PLA2 exists as a stable monomeric molecule in aqueous solution.The experimental data from ICP-AES reveal that the purified GBB-PLA2 is a Ca2+ bound protein with a calcium stoichiometry of 1:1([Ca2+]/[GBB-PLA2]).Removal of Ca2+ from GBB-PLA2 decreases the hydrolysis activity of PLA2 by 90%,suggesting that Ca2+ ions play a critical role for GBB-PLA2.The addition of exogenous Ca2+ can accelerate the hydrolysis rate of the substrate DPPC for GBB-PLA2.Ca2+ increases the thermostability by 3 ℃ and changes the secondary structure of GBB-PLA2,indicating that the presence of Ca2+ helps to maintain the structure integrity of GBB-PLA2.
2009, 26(3): 263-267
Abstract:
The objective of this work is to study the effect of molar mass of chitosan(CS) on its intercalation in Na+-montmorillonite.Chitosan/montmorillonite intercalate nanocomposites with chitosan of different molar masses were successfully prepared via solution-mixing technique.Their structures were characterized by XRD,TEM and FT-IR techniques.The results show that after it was treated by diluted acetic acid solution,the interlayer distance of montmorillonite could be expended to 1.55 nm compared to originally 1.3 nm because of the existence of acetic acid residue;the interlayer distance of layered silicates in the intercalate nanocompo-sites enlarged as molar mass of chitosan decreased.When the molar mass was 4.1×104,the largest interlayer distance of 2.48 nm was obtained.However,with further decrease of the molar mass,the interlayer distance of the layered silicates in the intercalate nanocomposites reduced.Strong static interaction among chitosan and montmorillonite existed in the intercalate nanocomposites.The thermal stability of the intercalate nanocompo-sites were characterized by TGA.Amount of chitosan content in the intercalate nanocomposites increased as molar mass of chitosan decreased.The thermal stability of CS in the intercalate nanocomposites decreased due to the acetic acid residue in the composite.
The objective of this work is to study the effect of molar mass of chitosan(CS) on its intercalation in Na+-montmorillonite.Chitosan/montmorillonite intercalate nanocomposites with chitosan of different molar masses were successfully prepared via solution-mixing technique.Their structures were characterized by XRD,TEM and FT-IR techniques.The results show that after it was treated by diluted acetic acid solution,the interlayer distance of montmorillonite could be expended to 1.55 nm compared to originally 1.3 nm because of the existence of acetic acid residue;the interlayer distance of layered silicates in the intercalate nanocompo-sites enlarged as molar mass of chitosan decreased.When the molar mass was 4.1×104,the largest interlayer distance of 2.48 nm was obtained.However,with further decrease of the molar mass,the interlayer distance of the layered silicates in the intercalate nanocomposites reduced.Strong static interaction among chitosan and montmorillonite existed in the intercalate nanocomposites.The thermal stability of the intercalate nanocompo-sites were characterized by TGA.Amount of chitosan content in the intercalate nanocomposites increased as molar mass of chitosan decreased.The thermal stability of CS in the intercalate nanocomposites decreased due to the acetic acid residue in the composite.
2009, 26(3): 268-272
Abstract:
Two new benzothiazole-pyrimidine chromophores were designed and synthesized.The structures of the molecules were characterized by IR,1H MNR,UV-Vis and so on.The second order nonlinear optical properties of both chromophores were determined by hyper Rayleigh scattering method.The results showed that the two new molecules exhibited excellent optic penetrability;the maximum absorption wavelengths of the compounds were less then 487 nm,and their critical wavelengths were below 550 nm.The compounds had high β values of 3.70×10-28 and 3.90×10-28 esu at 1 064 nm wavelength,respectively.These compounds were thermally stable with decomposition temperatures of 299 and 302 ℃,respectively,and consequently they could be considered for the preparation of NLO materials.
Two new benzothiazole-pyrimidine chromophores were designed and synthesized.The structures of the molecules were characterized by IR,1H MNR,UV-Vis and so on.The second order nonlinear optical properties of both chromophores were determined by hyper Rayleigh scattering method.The results showed that the two new molecules exhibited excellent optic penetrability;the maximum absorption wavelengths of the compounds were less then 487 nm,and their critical wavelengths were below 550 nm.The compounds had high β values of 3.70×10-28 and 3.90×10-28 esu at 1 064 nm wavelength,respectively.These compounds were thermally stable with decomposition temperatures of 299 and 302 ℃,respectively,and consequently they could be considered for the preparation of NLO materials.
2009, 26(3): 273-276
Abstract:
With cheap D,L-Lactic acid(D,L-LA) and valine(Val) as the stanting materials,and SnO as the catalyst,a novel biomaterial,poly(lactic acid-co-valine)[P(LAco-Val),was directly synthesized via melt copolycondensation.The copolymer was characterized with viscosity measurements,FTIR,1H NMR,DSC,XRD and GPC.The effects of feed molar ratio were discussed.When the feed molar ratio n(LA):n(Val) was 95:5,the weight-average molecular mass(Mw) was 7 300,the number-average molecular mass(Mn) was 5 400,which were all the highest.Its crystallinity(13.5%) was lower than that of homopolymer poly(D,L-lactic acid)(PDLLA).With the increase of the feed molar ratio of Val,Mw of the copolymer P(LA-co-Val) gradually became smaller,and the crystallinity gradually disappeared.But the lowest Mw of 1 800 and the glass-transition temperature(Tg) and the melting temperature(Tm) of the copolymer were similar to that of PDLLA,which could meet the requests for the application in drug delivery of this biodegradable material.
With cheap D,L-Lactic acid(D,L-LA) and valine(Val) as the stanting materials,and SnO as the catalyst,a novel biomaterial,poly(lactic acid-co-valine)[P(LAco-Val),was directly synthesized via melt copolycondensation.The copolymer was characterized with viscosity measurements,FTIR,1H NMR,DSC,XRD and GPC.The effects of feed molar ratio were discussed.When the feed molar ratio n(LA):n(Val) was 95:5,the weight-average molecular mass(Mw) was 7 300,the number-average molecular mass(Mn) was 5 400,which were all the highest.Its crystallinity(13.5%) was lower than that of homopolymer poly(D,L-lactic acid)(PDLLA).With the increase of the feed molar ratio of Val,Mw of the copolymer P(LA-co-Val) gradually became smaller,and the crystallinity gradually disappeared.But the lowest Mw of 1 800 and the glass-transition temperature(Tg) and the melting temperature(Tm) of the copolymer were similar to that of PDLLA,which could meet the requests for the application in drug delivery of this biodegradable material.
2009, 26(3): 277-281
Abstract:
Three anthraquinone secondary metabolites,(+)-3,3',7,7',8,8'-hexahydroxy-5,5'-dimethyl-bianthraquinone(compound 1),1,4,5-thihydroxy-7-methylanthraquinone(compound 2),and 1,6,8-thihydroxy-3-methylanthraquinone(compound 3),were isolated from the culture media of mangrove endo-phytic fungus #2240 collected from a mangrove Castaniopsic Fissa from South China Sea coast through chromatographic separation.Compound 1 was found for the first time.Their structures were elucidated based on related literature and spectral analyses including 1H/13C NMR,DEPT,HMQC,HMBC,HREIMS,IR,and UV-Vis.The DNA hTopo I isomerase inhibition test showed that compound 1 possessed strong activity,and the lowest inhibiting concentration(2.35×10-4 mol/L) was much less than that of the positive control camptothecin(1.00×10-3 mol/L).
Three anthraquinone secondary metabolites,(+)-3,3',7,7',8,8'-hexahydroxy-5,5'-dimethyl-bianthraquinone(compound 1),1,4,5-thihydroxy-7-methylanthraquinone(compound 2),and 1,6,8-thihydroxy-3-methylanthraquinone(compound 3),were isolated from the culture media of mangrove endo-phytic fungus #2240 collected from a mangrove Castaniopsic Fissa from South China Sea coast through chromatographic separation.Compound 1 was found for the first time.Their structures were elucidated based on related literature and spectral analyses including 1H/13C NMR,DEPT,HMQC,HMBC,HREIMS,IR,and UV-Vis.The DNA hTopo I isomerase inhibition test showed that compound 1 possessed strong activity,and the lowest inhibiting concentration(2.35×10-4 mol/L) was much less than that of the positive control camptothecin(1.00×10-3 mol/L).
2009, 26(3): 282-286
Abstract:
Graft polymerization of acrylic acid on starch was carried out via contact glow discharge electrolysis plasma(CGDE),and the product was characterized by Fourier transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA) and scanning electron microscopy(SEM).Five important factors for the graft polymerization were examined.For the contact glow discharge electrolysis plasma,the discharge time and the discharge power were also studied.At a discharge power of 12.8 W and a discharge time of 12 min,the optimum reaction conditions were obtained,namely,the ratio of acrylic acid to starch,the amount of crosslinking agent,reaction temperature,reaction time and neutralization of acrylic acid were 2:1,0.6%,70 ℃,3 h and 85%,respectively.A satisfactory starch-graft-acrylic acid superabsorbing resin with a graft percentage of 47% and a high absorbency(765 g/g in distilled water,81 g/g in 0.9% NaCl solution) was prepared successfully.
Graft polymerization of acrylic acid on starch was carried out via contact glow discharge electrolysis plasma(CGDE),and the product was characterized by Fourier transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA) and scanning electron microscopy(SEM).Five important factors for the graft polymerization were examined.For the contact glow discharge electrolysis plasma,the discharge time and the discharge power were also studied.At a discharge power of 12.8 W and a discharge time of 12 min,the optimum reaction conditions were obtained,namely,the ratio of acrylic acid to starch,the amount of crosslinking agent,reaction temperature,reaction time and neutralization of acrylic acid were 2:1,0.6%,70 ℃,3 h and 85%,respectively.A satisfactory starch-graft-acrylic acid superabsorbing resin with a graft percentage of 47% and a high absorbency(765 g/g in distilled water,81 g/g in 0.9% NaCl solution) was prepared successfully.
2009, 26(3): 287-291
Abstract:
A glassy carbon eletrode(GCE) was modified with electropolymerized films of valine by cyclic voltammetry(CV) in phosphate buffer solution(PBS) of pH=9.0 containning 0.01 mol/L valine and conditioned by cyclic sweeping from 1.0~2.4 V at 40 mV/s for 9 scans.The modified electrode showed an excellent electrocatalytical effect on the oxidation of norepinephrine(NE).The voltammetric behavior and electrochemical analysis method of NE were studied on the modified electrode.The effect of PBS pH value on the response of NE was studied in a pH value range of 2.2~8.0.The results show that the redox peak potential of NE shifts negatively with increasing of pH value and a pair of well-defined redox waves are observed in PBS of pH=4.0.The modified electrode was used to determine NE in an excess of ascorbic acid(AA) by reduction peak current of CV.The reduction peak currents increased linearly in two concentration ranges of NE,one is 4.6×10-7~1.1×10-5 mol/L,the other is 1.1×10-5~1.2×10-4 mol/L,correlation coefficients of which are 0.995 7 and 0.991 8 respectively,the detection limit(S/N=3) is 8.0×10-8 mol/L.The linear regression equations are ipc(A)=6.80×10-7+1.05c and ipc(A)=1.23×10-5+0.16c.The valine modified electrode showed good sensitivity,selectivity,stability.It was applied to the NE injection sample analysis.
A glassy carbon eletrode(GCE) was modified with electropolymerized films of valine by cyclic voltammetry(CV) in phosphate buffer solution(PBS) of pH=9.0 containning 0.01 mol/L valine and conditioned by cyclic sweeping from 1.0~2.4 V at 40 mV/s for 9 scans.The modified electrode showed an excellent electrocatalytical effect on the oxidation of norepinephrine(NE).The voltammetric behavior and electrochemical analysis method of NE were studied on the modified electrode.The effect of PBS pH value on the response of NE was studied in a pH value range of 2.2~8.0.The results show that the redox peak potential of NE shifts negatively with increasing of pH value and a pair of well-defined redox waves are observed in PBS of pH=4.0.The modified electrode was used to determine NE in an excess of ascorbic acid(AA) by reduction peak current of CV.The reduction peak currents increased linearly in two concentration ranges of NE,one is 4.6×10-7~1.1×10-5 mol/L,the other is 1.1×10-5~1.2×10-4 mol/L,correlation coefficients of which are 0.995 7 and 0.991 8 respectively,the detection limit(S/N=3) is 8.0×10-8 mol/L.The linear regression equations are ipc(A)=6.80×10-7+1.05c and ipc(A)=1.23×10-5+0.16c.The valine modified electrode showed good sensitivity,selectivity,stability.It was applied to the NE injection sample analysis.
2009, 26(3): 292-296
Abstract:
Iodine-sulfur(I-S) cycle is one of the most promising thermochemical water-splitting processes for massive hydrogen production in the future with a high heat to hydrogen conversion efficiency.In this work,the separation characteristics of the two phases,sulfuric acid phase and polyhydriodic acid(HIx) phase,formed in Bunsen reaction of the cycle,were investigated.The effects of temperature of the solution and molar fraction of iodine in the mixture of H2SO4 and HIx on the separation characteristics were studied.The influence of the molar ratio of iodine to water in the Bunsen reaction on the phase separation and saturation of I2 was studied.Results show that the addition of excess iodine causes the formation of two insoluble liquid phases,the amount of excess iodine for the phase separation increases with the increasing of temperature and reaches the highest at 60 ℃.The separation characteristics are notably affected by molar ratio of iodine to water.If n(I2):n(H2O)1:8,the two acids can not be separated;if n(I2):n(H2O)1:5,iodine in the products may solidify at room temperature.In addition,the concentrations of H+,I-,SO42- and I3- in the whole process of continuous SO2 addition were determined.Based on these results,possible reactions in Bunsen reaction were assumed and suitable reaction conditions were proposed.These results are beneficial to the selection of the operational parameters for Bunsen section of IS process.
Iodine-sulfur(I-S) cycle is one of the most promising thermochemical water-splitting processes for massive hydrogen production in the future with a high heat to hydrogen conversion efficiency.In this work,the separation characteristics of the two phases,sulfuric acid phase and polyhydriodic acid(HIx) phase,formed in Bunsen reaction of the cycle,were investigated.The effects of temperature of the solution and molar fraction of iodine in the mixture of H2SO4 and HIx on the separation characteristics were studied.The influence of the molar ratio of iodine to water in the Bunsen reaction on the phase separation and saturation of I2 was studied.Results show that the addition of excess iodine causes the formation of two insoluble liquid phases,the amount of excess iodine for the phase separation increases with the increasing of temperature and reaches the highest at 60 ℃.The separation characteristics are notably affected by molar ratio of iodine to water.If n(I2):n(H2O)1:8,the two acids can not be separated;if n(I2):n(H2O)1:5,iodine in the products may solidify at room temperature.In addition,the concentrations of H+,I-,SO42- and I3- in the whole process of continuous SO2 addition were determined.Based on these results,possible reactions in Bunsen reaction were assumed and suitable reaction conditions were proposed.These results are beneficial to the selection of the operational parameters for Bunsen section of IS process.
2009, 26(3): 297-301
Abstract:
Disproportionated rosin amine Schiff base was synthesized from disproportionated rosin amine.The ligand and its nickel complex were characterized with FTIR,UV,elemental analysis etc.The catalytic performance of the nickel complex for the oxidation of abietic acid was studied.The influences of solvent,H2O2 concentration,reaction temperature and time were investigated.The results show the catalyst has good catalytic performance for the oxidation and polymerization of abietic acid,and the conversion of abietic acid reaches to 100%.
Disproportionated rosin amine Schiff base was synthesized from disproportionated rosin amine.The ligand and its nickel complex were characterized with FTIR,UV,elemental analysis etc.The catalytic performance of the nickel complex for the oxidation of abietic acid was studied.The influences of solvent,H2O2 concentration,reaction temperature and time were investigated.The results show the catalyst has good catalytic performance for the oxidation and polymerization of abietic acid,and the conversion of abietic acid reaches to 100%.
2009, 26(3): 302-305
Abstract:
Barbalion in Aloe was determined by capillary electrophoresis coupled with amperometric detection(CE-AD).The pH,type and concentration of the running buffer,the detection potential,the applied voltage and the sampling time were selected as the investigated variables.Under the optimized conditions: a running buffer composed of 30 mmol/L Na2B4O7 buffer at pH 9.5,separation voltage at 15 kV,injection time 10 seconds,2.5% methanol additive and detection potential-0.8 V,a linearity existed between peak area(Y) and mass concentration of Barbalion(c) in a range of 0.05～50 mg/L,r=0.999 4,and the determination limit was 0.01 mg/L.
Barbalion in Aloe was determined by capillary electrophoresis coupled with amperometric detection(CE-AD).The pH,type and concentration of the running buffer,the detection potential,the applied voltage and the sampling time were selected as the investigated variables.Under the optimized conditions: a running buffer composed of 30 mmol/L Na2B4O7 buffer at pH 9.5,separation voltage at 15 kV,injection time 10 seconds,2.5% methanol additive and detection potential-0.8 V,a linearity existed between peak area(Y) and mass concentration of Barbalion(c) in a range of 0.05～50 mg/L,r=0.999 4,and the determination limit was 0.01 mg/L.
2009, 26(3): 306-310
Abstract:
The reactions between each of four isoflavone aglycones,including 7-hydroxy-isoflavone and 7-hydroxy-4'-methoxyl-isoflavone,which were prepared from Friedel-Crafts reactions,as well as 5,7-dihydroxy-4'-methoxyl-isoflavone and 5,7-dihydroxy-4'-chloride-isoflavone,which were prepared from Hoesch reactions,and 1-bromo-2,3,4,6-tetra-O-acetyl-D-glucopyranose in NaHCO3/KCl alkaline solutions in the presence of the phase transfer catalyst tri(3,6-dioxaheptyl)amine(TDA-1) were discussed.The corresponding glucosides formed were confirmed by IR,1H NMR and elemental analysis,with a yield of 64%,61%,55% and 58% respectively.
The reactions between each of four isoflavone aglycones,including 7-hydroxy-isoflavone and 7-hydroxy-4'-methoxyl-isoflavone,which were prepared from Friedel-Crafts reactions,as well as 5,7-dihydroxy-4'-methoxyl-isoflavone and 5,7-dihydroxy-4'-chloride-isoflavone,which were prepared from Hoesch reactions,and 1-bromo-2,3,4,6-tetra-O-acetyl-D-glucopyranose in NaHCO3/KCl alkaline solutions in the presence of the phase transfer catalyst tri(3,6-dioxaheptyl)amine(TDA-1) were discussed.The corresponding glucosides formed were confirmed by IR,1H NMR and elemental analysis,with a yield of 64%,61%,55% and 58% respectively.
2009, 26(3): 311-315
Abstract:
By means of UV spectrophotometry,ESI-MS and HPLC,the content of ginsenoside in ginseng was detected in order to evaluat the effects of plasma seed treating technique on ginseng.The optimal conditions of plasma seed treatment were given.For treated ginsengs,the content of ginsenosides showed normal distribution approximately with the increase of magnetic current.The total content of ginsenosides was relative high at magnetic current of 1.1~1.5 A,and the content of main ginsenosides obviously increased.Plasma-magnetic seed treating technique played an important role in promoting the ginsenoside content.In this work,a semi-quantitative method of electrospray ionization mass spectrometry has also been established,and this method can conveniently measure the content change of main ginsenosides in ginsengs for untreated and treated seeds.
By means of UV spectrophotometry,ESI-MS and HPLC,the content of ginsenoside in ginseng was detected in order to evaluat the effects of plasma seed treating technique on ginseng.The optimal conditions of plasma seed treatment were given.For treated ginsengs,the content of ginsenosides showed normal distribution approximately with the increase of magnetic current.The total content of ginsenosides was relative high at magnetic current of 1.1~1.5 A,and the content of main ginsenosides obviously increased.Plasma-magnetic seed treating technique played an important role in promoting the ginsenoside content.In this work,a semi-quantitative method of electrospray ionization mass spectrometry has also been established,and this method can conveniently measure the content change of main ginsenosides in ginsengs for untreated and treated seeds.
2009, 26(3): 316-320
Abstract:
Four new porphyrin-5-fluorouracil compounds were designed and synthesized with yields of 27.1%~58.3% and mp300 ℃.The reaction conditions were optimized,and the separation method of the target products was explored.The compositions and structures of these compounds were confirmed by IR,UV-Vis,1H NMR,and MS.The antitumor activity experimental results showed that D1,C2,D2 compounds inhibited distinctly the growth of cancer S180 in the mice.
Four new porphyrin-5-fluorouracil compounds were designed and synthesized with yields of 27.1%~58.3% and mp300 ℃.The reaction conditions were optimized,and the separation method of the target products was explored.The compositions and structures of these compounds were confirmed by IR,UV-Vis,1H NMR,and MS.The antitumor activity experimental results showed that D1,C2,D2 compounds inhibited distinctly the growth of cancer S180 in the mice.
2009, 26(3): 321-324
Abstract:
Water-soluble Cu-doped CdS nanocrystals were prepared in aqueous solution with thioglycolic acid as stabilizer.ICP-AES,atomic force microscope were used to characterize the chemical composition and shape of the product,respectively.The excitation and emission spectra of Cu-doped CdS nanocrystals were investigated.The results show that the shape of Cd0.99Cu0.01S was rod and granule after refluxing for 2 h.The experiment demonstrates that the maximal emission wavelength of CdS nanocrystals was red-shifted after Cu was doped.Before refluxing,the λmax of CdS was at 520 nm,but the λmax of Cd0.99Cu0.01S and Cd0.98Cu0.02S were red-shifted to 595 nm and 610 nm,respectively.The emission wavelength of CdS could be tuned by varying the content of Cu.
Water-soluble Cu-doped CdS nanocrystals were prepared in aqueous solution with thioglycolic acid as stabilizer.ICP-AES,atomic force microscope were used to characterize the chemical composition and shape of the product,respectively.The excitation and emission spectra of Cu-doped CdS nanocrystals were investigated.The results show that the shape of Cd0.99Cu0.01S was rod and granule after refluxing for 2 h.The experiment demonstrates that the maximal emission wavelength of CdS nanocrystals was red-shifted after Cu was doped.Before refluxing,the λmax of CdS was at 520 nm,but the λmax of Cd0.99Cu0.01S and Cd0.98Cu0.02S were red-shifted to 595 nm and 610 nm,respectively.The emission wavelength of CdS could be tuned by varying the content of Cu.
2009, 26(3): 325-328
Abstract:
To study the conditions and parameters for the purification of lycorine with macroporous adsorbent resin,the adsorption and desorption of nine macroporous adsorbent resins for lycorine were compared.The optimal adsorbent HPD300 and the appropriate adsorption/desorption conditions were determined,i.e.,the concentration of lycorine in extract solution was at 1.22 g/L,volume at 9BV was passed through the column at a flow rate of 2 BV/h and room temperature,the column was washed with 4 BV water at a flow rate of 2 BV/h,8 BV 70% alcohol was satisfactory eluant for desorption at a flow rate of 2 BV/h.The purity of lycorine was increased from 9.93% to 23.07%.
To study the conditions and parameters for the purification of lycorine with macroporous adsorbent resin,the adsorption and desorption of nine macroporous adsorbent resins for lycorine were compared.The optimal adsorbent HPD300 and the appropriate adsorption/desorption conditions were determined,i.e.,the concentration of lycorine in extract solution was at 1.22 g/L,volume at 9BV was passed through the column at a flow rate of 2 BV/h and room temperature,the column was washed with 4 BV water at a flow rate of 2 BV/h,8 BV 70% alcohol was satisfactory eluant for desorption at a flow rate of 2 BV/h.The purity of lycorine was increased from 9.93% to 23.07%.
2009, 26(3): 329-332
Abstract:
A novel β-diketone Schiff base was synthesized from acetylacetone and pentaerythrityl tetramine and characterized by elemental analysis,IR,1H NMR,MS and single crystal X-ray diffraction analysis.The crystal belongs to monoclinic system,and the space group is C2/c,with the crystal cell parameters a=1.238 9(2),b=1.348 3(2),c=1.566 9(3) nm,β=91.243(7)°,V=2.616 8(8) nm3,Z=4,Dc=1.169 g/cm3,Mr=460.61,R1=0.063 8,wR2=0.219 2.The structural analysis revealed that the tauto-merism of the Schiff base occurs in either chloroform solution or solid state,and 1D chains are formed via π-π stacking interactions and C—H-π interactions along the direction of the b axis.CCDC:673 957.
A novel β-diketone Schiff base was synthesized from acetylacetone and pentaerythrityl tetramine and characterized by elemental analysis,IR,1H NMR,MS and single crystal X-ray diffraction analysis.The crystal belongs to monoclinic system,and the space group is C2/c,with the crystal cell parameters a=1.238 9(2),b=1.348 3(2),c=1.566 9(3) nm,β=91.243(7)°,V=2.616 8(8) nm3,Z=4,Dc=1.169 g/cm3,Mr=460.61,R1=0.063 8,wR2=0.219 2.The structural analysis revealed that the tauto-merism of the Schiff base occurs in either chloroform solution or solid state,and 1D chains are formed via π-π stacking interactions and C—H-π interactions along the direction of the b axis.CCDC:673 957.
2009, 26(3): 333-336
Abstract:
The feasibility of enhanced desulfurizing flotation of coal was investigated by sonoelectrochemical method.The electrolyte was calcium hydroxide,the additive was ethanol.The effects of treating conditions,including the concentration of anhydrous ethanol,sonoelectrolytic time,concentration of calcium hydroxide,current density,ultrasound intensity on desulfurization were studied by single factor method.The optimal experimental conditions of 2.04 mol/L,40 min,2.0 g/L,7.5×10-3 A/cm2 and 1.23 W/cm2 were achieved.Under the optimal conditions,the desulfurization could be up to 82.72%.The raw coal and the coal sample treated with sonoelectrochemical method were analysed via infrared spectroscopy.The result shows the desulfurizing flotation of coal by sonoelectrochemical method is effective.
The feasibility of enhanced desulfurizing flotation of coal was investigated by sonoelectrochemical method.The electrolyte was calcium hydroxide,the additive was ethanol.The effects of treating conditions,including the concentration of anhydrous ethanol,sonoelectrolytic time,concentration of calcium hydroxide,current density,ultrasound intensity on desulfurization were studied by single factor method.The optimal experimental conditions of 2.04 mol/L,40 min,2.0 g/L,7.5×10-3 A/cm2 and 1.23 W/cm2 were achieved.Under the optimal conditions,the desulfurization could be up to 82.72%.The raw coal and the coal sample treated with sonoelectrochemical method were analysed via infrared spectroscopy.The result shows the desulfurizing flotation of coal by sonoelectrochemical method is effective.
2009, 26(3): 337-341
Abstract:
Adsorption of ethyl acetate(EA) on activated carbons at 40 ℃ was investigated to find the effects of pore structure,surface properties and relative humidity on the adsorption of EA.It was found that the adsorption capacity of activated carbons for EA is mainly determined by micropore structure(1.70 nm) but not surface chemistry of the adsorbents.The saturated adsorption amounts of EA on the activated carbons AC and Y2 with abundant micropore area were 0.31 g/g and 0.28 g/g,respectively,in the gas mixture of EA/N2 with a concentration of 0.30% in volume percentage(φ(EA)).A saturated adsorption amount as high as 90% of that achieved under dry conditions was still obtained even when an adsorption experiment was conducted at a relative humidity of 40%.Regeneration of activated carbon and the recovery of EA could be effectively completed by heating the absorbent to 180 ℃ after adsorption.The adsorption property of the adsorbent for EA was not influenced by little O2 in the gas flow used for the adsorbent regeneration.Activated carbon could be well used repeatedly as an adsorbent for EA adsorption after the regeneration without change in property for EA adsorption.
Adsorption of ethyl acetate(EA) on activated carbons at 40 ℃ was investigated to find the effects of pore structure,surface properties and relative humidity on the adsorption of EA.It was found that the adsorption capacity of activated carbons for EA is mainly determined by micropore structure(1.70 nm) but not surface chemistry of the adsorbents.The saturated adsorption amounts of EA on the activated carbons AC and Y2 with abundant micropore area were 0.31 g/g and 0.28 g/g,respectively,in the gas mixture of EA/N2 with a concentration of 0.30% in volume percentage(φ(EA)).A saturated adsorption amount as high as 90% of that achieved under dry conditions was still obtained even when an adsorption experiment was conducted at a relative humidity of 40%.Regeneration of activated carbon and the recovery of EA could be effectively completed by heating the absorbent to 180 ℃ after adsorption.The adsorption property of the adsorbent for EA was not influenced by little O2 in the gas flow used for the adsorbent regeneration.Activated carbon could be well used repeatedly as an adsorbent for EA adsorption after the regeneration without change in property for EA adsorption.
2009, 26(3): 342-345
Abstract:
A series of novel poly(aryl ether ketone)s with zao-units were prepared by low temperature Friedal-Crafts polycondensation of azobenzide diformylchloride and aromatic diethers with pendant cyano groups in the presence of AlCl3,DCE and NMP.IR,DSC,TG and elemental analysis techniques were used to characterize the polymers.The resulted polymers had the proposed structures and their Td values in N2 were 426～452 ℃,indicating that the polymers had good heat-resistance properties.In addition,the polymers can be dissolved in aprotic polar organic solvents(NMP,DMSO and DMF) and some common solvents(DCE,CHCl3,and THF) as well as in strong protic acid,such as aqueous sulfuric acid,and in CHCl3/CF3COOH mixtures.
A series of novel poly(aryl ether ketone)s with zao-units were prepared by low temperature Friedal-Crafts polycondensation of azobenzide diformylchloride and aromatic diethers with pendant cyano groups in the presence of AlCl3,DCE and NMP.IR,DSC,TG and elemental analysis techniques were used to characterize the polymers.The resulted polymers had the proposed structures and their Td values in N2 were 426～452 ℃,indicating that the polymers had good heat-resistance properties.In addition,the polymers can be dissolved in aprotic polar organic solvents(NMP,DMSO and DMF) and some common solvents(DCE,CHCl3,and THF) as well as in strong protic acid,such as aqueous sulfuric acid,and in CHCl3/CF3COOH mixtures.
2009, 26(3): 346-348
Abstract:
Two enantionmetric unsaturated amino acids were asymmetrically synthesized with Gly-Ni-2[N-(N'-benzylprolyl)amino]benzophenone and Ala-Ni-2[N-(N'-benzylprolyl)amino]benzophenone as chiral auxiliary to undergo replacement reaction with 3-bromopropene.The yields of two intermediates were 90%~93% and the yields of the amino acids were 75% and 80% respectively.The recovery of the Chiral auxiliary 2-[N-(N'-benzylprolyl)]-aminobenzophenone was over 90% without any loss of optical purity.All the products were characterized by NMR,MS,and optical rotation.
Two enantionmetric unsaturated amino acids were asymmetrically synthesized with Gly-Ni-2[N-(N'-benzylprolyl)amino]benzophenone and Ala-Ni-2[N-(N'-benzylprolyl)amino]benzophenone as chiral auxiliary to undergo replacement reaction with 3-bromopropene.The yields of two intermediates were 90%~93% and the yields of the amino acids were 75% and 80% respectively.The recovery of the Chiral auxiliary 2-[N-(N'-benzylprolyl)]-aminobenzophenone was over 90% without any loss of optical purity.All the products were characterized by NMR,MS,and optical rotation.
2009, 26(3): 349-351
Abstract:
This paper describes the phase state of active species of bi-component catalyst composed of titanocene complex and nano-NaH for the hydrogenation of olefins.When the reaction mixture was separated into soluble and insoluble parts,it was found that the soluble part was not catalytic ally active,while the insoluble part was active,and the catalytical efficiency(turnover,TO) was up to 2 800 for the hydrogenation of olefins.A further study by UV technique showed that the absorbency of titanocene characteristic peak(2.3) for the insoluble part was much stronger than that for the soluble part.It is evident that most of the Ti species was adsorbed in situ on the surface of nano-NaH,and only a small part of them existed in solution.Nano-NaH act both as a reducing agent and a catalyst carrier for the Ti species.The supported catalytic active species of Ti showed a much better activity and stability than their homogeneous counterpart.
This paper describes the phase state of active species of bi-component catalyst composed of titanocene complex and nano-NaH for the hydrogenation of olefins.When the reaction mixture was separated into soluble and insoluble parts,it was found that the soluble part was not catalytic ally active,while the insoluble part was active,and the catalytical efficiency(turnover,TO) was up to 2 800 for the hydrogenation of olefins.A further study by UV technique showed that the absorbency of titanocene characteristic peak(2.3) for the insoluble part was much stronger than that for the soluble part.It is evident that most of the Ti species was adsorbed in situ on the surface of nano-NaH,and only a small part of them existed in solution.Nano-NaH act both as a reducing agent and a catalyst carrier for the Ti species.The supported catalytic active species of Ti showed a much better activity and stability than their homogeneous counterpart.
2009, 26(3): 352-354
Abstract:
Bis(indolyl)methanes can be prepared rapidly in good yields(69%~95%) from indole and aldehyde or ketone in the presence of phosphotungstic acid as a catalyst.Their structures were confirmed by IR,1H NMR,13C NMR,MS and elemental analysis.
Bis(indolyl)methanes can be prepared rapidly in good yields(69%~95%) from indole and aldehyde or ketone in the presence of phosphotungstic acid as a catalyst.Their structures were confirmed by IR,1H NMR,13C NMR,MS and elemental analysis.
2009, 26(3): 355-357
Abstract:
Several chiral medicines were separated on a new home-made β-cyclodextrins chiral stationary phase.The perphenylcarbamoylated β-cyclodextrin bonded silica CSP was prepared step by step,from synthesized and purified mono-6-p-toluenesulfonyl-β-cyclodextrin,mono-6-N-allylamino-β-cyclodextrin and mono-6-Nβ-cyclodextrin.By this CSP,baseline separation of five racemic medicines(fluoxetine,paroxetine,naproxen,propranolol and alprenolol) was realized.The optimal conditions were determined.The mobile phase was methanol-0.15%TEAA(35:65,V/V,pH=4.0) for paroxetine and naproxen,methanol-0.15%TEAA(30:70,V/V,pH=4.0) for fluoxetine,and methanol-0.15%TEAA(40:60,V/V,pH=5.0) for propranolol and alprenolol,respectively;the flowrate was 0.5 mL/min,the temperature 20 ℃,and UV-detector was used(254 nm).
Several chiral medicines were separated on a new home-made β-cyclodextrins chiral stationary phase.The perphenylcarbamoylated β-cyclodextrin bonded silica CSP was prepared step by step,from synthesized and purified mono-6-p-toluenesulfonyl-β-cyclodextrin,mono-6-N-allylamino-β-cyclodextrin and mono-6-Nβ-cyclodextrin.By this CSP,baseline separation of five racemic medicines(fluoxetine,paroxetine,naproxen,propranolol and alprenolol) was realized.The optimal conditions were determined.The mobile phase was methanol-0.15%TEAA(35:65,V/V,pH=4.0) for paroxetine and naproxen,methanol-0.15%TEAA(30:70,V/V,pH=4.0) for fluoxetine,and methanol-0.15%TEAA(40:60,V/V,pH=5.0) for propranolol and alprenolol,respectively;the flowrate was 0.5 mL/min,the temperature 20 ℃,and UV-detector was used(254 nm).
2009, 26(3): 358-360
Abstract:
Saponins of panax japonicus was determined by spectrophotometry at 571 nm wavelength with ginsenoside Rb1 as a reference.The results showed linearity between the quantity and the absorbance,and the linear range of saponins was 100~600 μg.The regression equation was Y=392.47x+104.18(R2=0.998 5).The average recovery rate was 99.54% and the RSD was 0.97%.The method is comparable to HPLC.The method is simple,rapid and accurate.
Saponins of panax japonicus was determined by spectrophotometry at 571 nm wavelength with ginsenoside Rb1 as a reference.The results showed linearity between the quantity and the absorbance,and the linear range of saponins was 100~600 μg.The regression equation was Y=392.47x+104.18(R2=0.998 5).The average recovery rate was 99.54% and the RSD was 0.97%.The method is comparable to HPLC.The method is simple,rapid and accurate.
2009, 26(3): 361-363
Abstract:
GTA(Glycidyl-triethylammonium chloride) was synthesized by using triethylamine instead of trimethylamine under ultrasonic condition.The reaction was under better controlled when liquid tertiary amine was used.The reaction time was decreased when ultrasonic technology was applied.The best conditions for the synthesis of GTA were: ultrasound frequency was 40 kHz,the reaction temperature was 25 ℃,n(EPIC):(TEA) was 1:1.5,pH value was 7~7.5,the reaction time was 0.5 h.The yield was 97.61%,epoxy value was 91.57%,melting point was 138~140 ℃.
GTA(Glycidyl-triethylammonium chloride) was synthesized by using triethylamine instead of trimethylamine under ultrasonic condition.The reaction was under better controlled when liquid tertiary amine was used.The reaction time was decreased when ultrasonic technology was applied.The best conditions for the synthesis of GTA were: ultrasound frequency was 40 kHz,the reaction temperature was 25 ℃,n(EPIC):(TEA) was 1:1.5,pH value was 7~7.5,the reaction time was 0.5 h.The yield was 97.61%,epoxy value was 91.57%,melting point was 138~140 ℃.
2009, 26(3): 364-366
Abstract:
A method for determination of the contents of residual methanol,n-hexane,acetonitrile in solanesol by gas chromatography was reported.Samples and reference substances were dissolved in isopropanol,and tetrahydrofuran was used as the internal standard.A HP-5MS quartz capillary column(5% phenyl siloxane-95% methyl polyorganosiloxane,30 m×0.25 mm×0.25 μm) and FID detector was used.The temperature of the column was kept at 80 ℃ for 5 min,and then raised to 120 ℃ at 8 ℃/min,at which the sample was kept for 10 min.The temperature of the vaporizing chamber and the injection port was 200 ℃ and 250 ℃,respectively.High purity nitrogen was used as the carrier gas at a flow rate of 2.0 mL/min,and the volume of injection was 2 μL.
A method for determination of the contents of residual methanol,n-hexane,acetonitrile in solanesol by gas chromatography was reported.Samples and reference substances were dissolved in isopropanol,and tetrahydrofuran was used as the internal standard.A HP-5MS quartz capillary column(5% phenyl siloxane-95% methyl polyorganosiloxane,30 m×0.25 mm×0.25 μm) and FID detector was used.The temperature of the column was kept at 80 ℃ for 5 min,and then raised to 120 ℃ at 8 ℃/min,at which the sample was kept for 10 min.The temperature of the vaporizing chamber and the injection port was 200 ℃ and 250 ℃,respectively.High purity nitrogen was used as the carrier gas at a flow rate of 2.0 mL/min,and the volume of injection was 2 μL.
2009, 26(3): 367-369
Abstract:
Hybrid 3DOM SiO2-NH2 materials with different amino contents have been prepared with(3-aminoproyl)triethoxysilane(APTES) and tetraethoxysilane(TEOS) as precursors and PS colloidal crystal as a template.SEM observations showed that the macropores were highly ordered and interconnected by small windows.The mean pore diameters of the materials were between 535 and 596 nm,and the pore shrinkage was between 4.8% and 14.5%.The surface area of the material was 10.2 m2/g.FTIR measurements showed that there were amino and organic groups in the pore walls.Adsorption capability of the materials were investigated with Cr(Ⅵ) ion as the adsorbate.The results showed that the adsorption quantity increased with the amount of the amino group in the material and the maximal adsorption quantity was 4.31 mmol/g.
Hybrid 3DOM SiO2-NH2 materials with different amino contents have been prepared with(3-aminoproyl)triethoxysilane(APTES) and tetraethoxysilane(TEOS) as precursors and PS colloidal crystal as a template.SEM observations showed that the macropores were highly ordered and interconnected by small windows.The mean pore diameters of the materials were between 535 and 596 nm,and the pore shrinkage was between 4.8% and 14.5%.The surface area of the material was 10.2 m2/g.FTIR measurements showed that there were amino and organic groups in the pore walls.Adsorption capability of the materials were investigated with Cr(Ⅵ) ion as the adsorbate.The results showed that the adsorption quantity increased with the amount of the amino group in the material and the maximal adsorption quantity was 4.31 mmol/g.
2009, 26(3): 370-372
Abstract:
Sodium allylate was prepared from solid sodium hydroxide and allyl alcohol under mild conditions,and then the solid sodium allylate was reacted with epichlorohydrin in anhydrous system to produce allyl glycidyl ether in high yield and purity.Effects of ratio of sodium allylate to epichlorohydrin,reaction temperature and time and way of adding materials on the yield of allyl glycidyl ether were investigated.Sodium allylate can be obtained in a high yield when the molar ratio of solid sodium hydroxide to allyl alcohol was 1 to 3.The yield of allyl glycidyl ether can reach up to 96% at 30 ℃ for 3 h at a molar ratio of 1 to 1.5 of sodium allylate to epichlorohydrin.
Sodium allylate was prepared from solid sodium hydroxide and allyl alcohol under mild conditions,and then the solid sodium allylate was reacted with epichlorohydrin in anhydrous system to produce allyl glycidyl ether in high yield and purity.Effects of ratio of sodium allylate to epichlorohydrin,reaction temperature and time and way of adding materials on the yield of allyl glycidyl ether were investigated.Sodium allylate can be obtained in a high yield when the molar ratio of solid sodium hydroxide to allyl alcohol was 1 to 3.The yield of allyl glycidyl ether can reach up to 96% at 30 ℃ for 3 h at a molar ratio of 1 to 1.5 of sodium allylate to epichlorohydrin.
