Login In
2013 Volume 30 Issue 3
2013, 30(3): 245-251
doi: 10.3724/SP.J.1095.2013.20430
Abstract:
The mechanisms of toughening polypropylene(PP) via the incorporation of inorganic rigid particles(IRP) were briefly summarized. The influence of PP matrix,properties and content of IRP,the dispersion of IRP within PP,as well as the interfacial interaction between IRP and PP matrix on toughening by IRP were emphatically introduced.
The mechanisms of toughening polypropylene(PP) via the incorporation of inorganic rigid particles(IRP) were briefly summarized. The influence of PP matrix,properties and content of IRP,the dispersion of IRP within PP,as well as the interfacial interaction between IRP and PP matrix on toughening by IRP were emphatically introduced.
2013, 30(3): 252-259
doi: 10.3724/SP.J.1095.2013.20188
Abstract:
Chitosan grafted poly(methacrylic acid)(CS-g-PMAA) was synthesized using methacrylic acid and chitosan as precursors and cerium ammonium nitrate as initiator.Products with different grafting degree were characterized by means of FTIR,1H NMR and elemental analysis.Drug-loaded beads made from the as-prepared copolymers were fabricated by combining ionic-crosslink with chemical-crosslink using trisodium citrate and glutaraldehyde as crosslinking agent,respectively.The beads have a core-shell structure as revealed from scanning electron microscopy.The release behaviors of model drug incorporated in the beads were monitored using UV/Vis spectrophotometer and found to be dependent on pH and NaCl content.The results show that the drug release rate is slowest for CS-g-PMAA beads with grafting fraction (Gg) of 12.21%.The total drug release fraction for the CS-g-PMAA beads is 44.18% at pH=1.8 and is less than that of CS beads,which is 65.24%.Therefore,the grafting of CS could improve the drug release behavior.In addition,CS-g-PMAA beads have higher enzymatic stability than that of CS beads.
Chitosan grafted poly(methacrylic acid)(CS-g-PMAA) was synthesized using methacrylic acid and chitosan as precursors and cerium ammonium nitrate as initiator.Products with different grafting degree were characterized by means of FTIR,1H NMR and elemental analysis.Drug-loaded beads made from the as-prepared copolymers were fabricated by combining ionic-crosslink with chemical-crosslink using trisodium citrate and glutaraldehyde as crosslinking agent,respectively.The beads have a core-shell structure as revealed from scanning electron microscopy.The release behaviors of model drug incorporated in the beads were monitored using UV/Vis spectrophotometer and found to be dependent on pH and NaCl content.The results show that the drug release rate is slowest for CS-g-PMAA beads with grafting fraction (Gg) of 12.21%.The total drug release fraction for the CS-g-PMAA beads is 44.18% at pH=1.8 and is less than that of CS beads,which is 65.24%.Therefore,the grafting of CS could improve the drug release behavior.In addition,CS-g-PMAA beads have higher enzymatic stability than that of CS beads.
2013, 30(3): 260-264
doi: 10.3724/SP.J.1095.2013.20164
Abstract:
Four amphiphilic bifunctionalized β-cyclodextrin derivatives with low degree of substitution(DS) were conveniently synthesized via the reaction of 2-O-(2-hydroxypropyl)-β-cyclodextrin with Lauryl glycidol ether,tetradecyl glycidol ether,hexadecyl glycidol ether and octadecyl glycidol ether in pyridine,respectively.The four amphiphilic β-CD derivatives(DS 1.87,1.95,2.14 and 1.80,respectively) could self-assemble in water to form stable nanospheres with improved dispersion degree and uniformity up to 2~3 weeks.
Four amphiphilic bifunctionalized β-cyclodextrin derivatives with low degree of substitution(DS) were conveniently synthesized via the reaction of 2-O-(2-hydroxypropyl)-β-cyclodextrin with Lauryl glycidol ether,tetradecyl glycidol ether,hexadecyl glycidol ether and octadecyl glycidol ether in pyridine,respectively.The four amphiphilic β-CD derivatives(DS 1.87,1.95,2.14 and 1.80,respectively) could self-assemble in water to form stable nanospheres with improved dispersion degree and uniformity up to 2~3 weeks.
2013, 30(3): 265-270
doi: 10.3724/SP.J.1095.2013.20161
Abstract:
A series of polyamine derivatives of naphthalimide(3a-3d) to be used as antitumor agents was synthesized.The biological and spectroscopic evaluations showed that compounds 3a-3d could used as DNA intercalators and had stronger cytotoxic activity and better selectivity than those of amonafide against cancer cells in vitro.The IC50 for antiproliferative activity of compound 3b on four cancer cells were 7.80,5.08,9.78 and 9.27 μmol/L,respectively.High content screening(HCS) results revealed that the as-prepared compounds might produce cytotoxicity through apoptosis via mitochondrial pathway.
A series of polyamine derivatives of naphthalimide(3a-3d) to be used as antitumor agents was synthesized.The biological and spectroscopic evaluations showed that compounds 3a-3d could used as DNA intercalators and had stronger cytotoxic activity and better selectivity than those of amonafide against cancer cells in vitro.The IC50 for antiproliferative activity of compound 3b on four cancer cells were 7.80,5.08,9.78 and 9.27 μmol/L,respectively.High content screening(HCS) results revealed that the as-prepared compounds might produce cytotoxicity through apoptosis via mitochondrial pathway.
2013, 30(3): 271-275
doi: 10.3724/SP.J.1095.2013.20211
Abstract:
The catalytic activities of ten dialkyltin compounds containing silicon were investigated through the condensation reaction of acetal(ketal)-alcohol.Factors such as amount of catalyst,reaction time,molar ratio of aldehyde(ketone) to alcohol and solvent kind were studied toward the yield of reaction.The results show that,except one catalyst,nine compounds are good in catalytic activities for the acetalization and ketalization.The yield reached 92% and 86% under optimal compounds:catalyst dosage was 1.4% based on the mass of the reactants,the molar ratio of the aldehyde to goycol was 1:1.3,ketone to goycol was 1:1.9,cyclohexane was used as the water carrying agent,and the reaction was refluxed for 3 h.
The catalytic activities of ten dialkyltin compounds containing silicon were investigated through the condensation reaction of acetal(ketal)-alcohol.Factors such as amount of catalyst,reaction time,molar ratio of aldehyde(ketone) to alcohol and solvent kind were studied toward the yield of reaction.The results show that,except one catalyst,nine compounds are good in catalytic activities for the acetalization and ketalization.The yield reached 92% and 86% under optimal compounds:catalyst dosage was 1.4% based on the mass of the reactants,the molar ratio of the aldehyde to goycol was 1:1.3,ketone to goycol was 1:1.9,cyclohexane was used as the water carrying agent,and the reaction was refluxed for 3 h.
2013, 30(3): 276-282
doi: 10.3724/SP.J.1095.2013.20185
Abstract:
Firstly,the Friedel-Crafts alkylation between the chloromethylated crosslinked polystyrene(CMCPS) microspheres and 2-hydroxy-4-methoxybenzaldehyde(HMBA) was carried out to afford the modified microspheres HMBA-CPS.Subsequently,the Schiff base reaction between HMBA-CPS and diaminocyclohexane was performed,leading to the microspheres Salen-CPS,on which Salen ligands were bonded.Finally,the coordination-chelating reaction of Salen-CPS with Mn salt was conducted,resulting in solid catalyst Mn(Ⅲ)Salen-CPS,on which chiral Mn(Ⅲ)-Salen complex was immobilized.The microspheres Salen-CPS and Mn(Ⅲ)Salen-CPS were fully characterized by methods such as FTIR,UV-Vis and SEM.The Friedel-Crafts alkylation between CMCPS microspheres and HMBA was mainly investigated because it was a key reaction.The results show that the Friedel-Crafts alkylation can be carried out when AlCl3 was used as Lewis catalyst and a mixture of dichloromethane and nitrobenzene was used as solvent.The new route is simple,convenient,direct and efficient.Under the suitable reaction conditions(volume ratio of dichloromethane to nitrobenzene=10:1,temperature=40℃,and reaction time=10 h),modified microspheres HMBA-CPS capable of converting chloromethyl with a 51% rate can be obtained.
Firstly,the Friedel-Crafts alkylation between the chloromethylated crosslinked polystyrene(CMCPS) microspheres and 2-hydroxy-4-methoxybenzaldehyde(HMBA) was carried out to afford the modified microspheres HMBA-CPS.Subsequently,the Schiff base reaction between HMBA-CPS and diaminocyclohexane was performed,leading to the microspheres Salen-CPS,on which Salen ligands were bonded.Finally,the coordination-chelating reaction of Salen-CPS with Mn salt was conducted,resulting in solid catalyst Mn(Ⅲ)Salen-CPS,on which chiral Mn(Ⅲ)-Salen complex was immobilized.The microspheres Salen-CPS and Mn(Ⅲ)Salen-CPS were fully characterized by methods such as FTIR,UV-Vis and SEM.The Friedel-Crafts alkylation between CMCPS microspheres and HMBA was mainly investigated because it was a key reaction.The results show that the Friedel-Crafts alkylation can be carried out when AlCl3 was used as Lewis catalyst and a mixture of dichloromethane and nitrobenzene was used as solvent.The new route is simple,convenient,direct and efficient.Under the suitable reaction conditions(volume ratio of dichloromethane to nitrobenzene=10:1,temperature=40℃,and reaction time=10 h),modified microspheres HMBA-CPS capable of converting chloromethyl with a 51% rate can be obtained.
2013, 30(3): 283-289
doi: 10.3724/SP.J.1095.2013.20179
Abstract:
Chloromethylation reaction of polysulfone(PSF) was performed with 1,4-bis(chloromethoxy)butane(BCMB) as chloromethylation reagent,leading to the formation of chloromethylated polysulfone(CMPSF).Subsequently,the nucleophilic substitution reaction between the chloromethyl group of CMPSF and phenolic hydroxyl group of 6-hydroxy-2-naphthoic acid(HNA) was performed,and the ligand of naphthoic acid(NA) was bonded on the side chains of polysulfone,resulting in naphthoic acid-functionalized polysulfone NAPSF.The chemical structure of NAPSF was characterized by FTIR and 1H NMR spectroscopies.The effects of the main factors on the nucleophilic substitution reaction between CMPSF and HNA were examined,the reaction mechanism was investigated,and the reaction conditions were optimized.Results show that the rate of the nucleophilic substitution reaction is independent of the concentration of the nucleophile HNA,indicating that this is a typical unimolecular nucleophilic substitution reaction,i.e.,SN1.The solvent polarity is favorable for the cleavage of C-Cl bond of the benzyl chloride group,and can accelerate the substitution reaction.Therefore,dimethylsulfoxide(DMSO) with stronger polarity is a suitable solvent.Under the suitable conditions,the conversion of chloromethyl group of CMPSF can reach 96%,and the corresponding bonding degree of NA is 1.68 mmol/g.The coordination reaction between NAPSF and Eu3+ ion was carried out for preparing the polymer-rare earth complex of NAPSF-Eu(Ⅲ),which exhibited the characteristic fluorescence emission spectrum of Eu3+ ion.More significantly,the macromolecular ligand NAPSF can strongly sensitize the fluorescence-emission of Eu3+ ion.
Chloromethylation reaction of polysulfone(PSF) was performed with 1,4-bis(chloromethoxy)butane(BCMB) as chloromethylation reagent,leading to the formation of chloromethylated polysulfone(CMPSF).Subsequently,the nucleophilic substitution reaction between the chloromethyl group of CMPSF and phenolic hydroxyl group of 6-hydroxy-2-naphthoic acid(HNA) was performed,and the ligand of naphthoic acid(NA) was bonded on the side chains of polysulfone,resulting in naphthoic acid-functionalized polysulfone NAPSF.The chemical structure of NAPSF was characterized by FTIR and 1H NMR spectroscopies.The effects of the main factors on the nucleophilic substitution reaction between CMPSF and HNA were examined,the reaction mechanism was investigated,and the reaction conditions were optimized.Results show that the rate of the nucleophilic substitution reaction is independent of the concentration of the nucleophile HNA,indicating that this is a typical unimolecular nucleophilic substitution reaction,i.e.,SN1.The solvent polarity is favorable for the cleavage of C-Cl bond of the benzyl chloride group,and can accelerate the substitution reaction.Therefore,dimethylsulfoxide(DMSO) with stronger polarity is a suitable solvent.Under the suitable conditions,the conversion of chloromethyl group of CMPSF can reach 96%,and the corresponding bonding degree of NA is 1.68 mmol/g.The coordination reaction between NAPSF and Eu3+ ion was carried out for preparing the polymer-rare earth complex of NAPSF-Eu(Ⅲ),which exhibited the characteristic fluorescence emission spectrum of Eu3+ ion.More significantly,the macromolecular ligand NAPSF can strongly sensitize the fluorescence-emission of Eu3+ ion.
2013, 30(3): 290-294
doi: 10.3724/SP.J.1095.2013.20131
Abstract:
Using pyrrole and p-nitrobenzaldehyde as the starting materials,a novel conjugated product of meso-tetra[4-(benzylideneamino)phenyl] porphyrin(TBAPP) was designed and synthesized after cyclization,reduction and condensation reactions.The product was characterized by UV-Vis,FT-IR,1H NMR determinations and elemental analysis.In addition,this porphyrin product was also investigated by fluorescence(FL) and electron paramagnetic resonance(EPR) methods.EPR measurement indicated that the prepared porphyrin molecule exhibited radical characteristics.The radicals were produced by the peripheral groups,which could be stabilized by the conjugated π-electrons of porphyrin molecule and detected under normal conditions.Meanwhile the substituent groups around the porphyrin ring contributed different influences on the spectral characters of UV-visible,fluorescence and electron paramagnetic resonance.Compare with its precursor of tetra-aminophenyl porpyrin(TAPP) and its parent compound of tetra-nitrophenyl porpyrin(TNPP),Q bands of the Schiff base phenyl porphyrin TBAPP shifted towards red direction,while its Soret band kept changeless;meanwhile,under excitation at λEx=440 nm,its emission peak appeared at λEm=658 nm,with 5 nm and 5 nm blue shift than those of TAPP and TNPP;furthermore its EPR fine structure was weaker than TAPP and stronger than TNPP.
Using pyrrole and p-nitrobenzaldehyde as the starting materials,a novel conjugated product of meso-tetra[4-(benzylideneamino)phenyl] porphyrin(TBAPP) was designed and synthesized after cyclization,reduction and condensation reactions.The product was characterized by UV-Vis,FT-IR,1H NMR determinations and elemental analysis.In addition,this porphyrin product was also investigated by fluorescence(FL) and electron paramagnetic resonance(EPR) methods.EPR measurement indicated that the prepared porphyrin molecule exhibited radical characteristics.The radicals were produced by the peripheral groups,which could be stabilized by the conjugated π-electrons of porphyrin molecule and detected under normal conditions.Meanwhile the substituent groups around the porphyrin ring contributed different influences on the spectral characters of UV-visible,fluorescence and electron paramagnetic resonance.Compare with its precursor of tetra-aminophenyl porpyrin(TAPP) and its parent compound of tetra-nitrophenyl porpyrin(TNPP),Q bands of the Schiff base phenyl porphyrin TBAPP shifted towards red direction,while its Soret band kept changeless;meanwhile,under excitation at λEx=440 nm,its emission peak appeared at λEm=658 nm,with 5 nm and 5 nm blue shift than those of TAPP and TNPP;furthermore its EPR fine structure was weaker than TAPP and stronger than TNPP.
2013, 30(3): 295-299
doi: 10.3724/SP.J.1095.2013.20150
Abstract:
5-Chlorosalicylaldehyde-2-aminoethanol-copper(Ⅱ) was synthesized using 5-chlorosalicylaldehyde,2-aminoethanol and cupric chloride as precursors under microwave irradiation. The product was characterized by IR spectra,elemental analysis and single X-ray crystallography study. The title complex crystallizes in the monoclinic space group P21/n. Cell parameters:a=0.49793(6) nm,b=1.7037(2) nm,c=1.07120(12) nm,β=94.579(3)°,F(000)=470,Z=2,V=0.905(8) nm3,Dc=1.689 mg/m3,R[I>2σ(I)],R1=0.0624,ωR2=0.1555. The Cu(Ⅱ) adopts a square planar configuration coordinated by two nitrogen atoms and two oxygen atoms from two Schiff bases. The antibacterial (B.subtilis, S.aureus, S.faecalis, P.aeruginosa, E.coli and E.cloacae) activities of the compounds were assayed by MTT (3-(4,5-dimethylthiazol-2-yl) -2,5-diphenyl tetrazolium bromide) method. It showed favorable antimicrobial activity with minimal inhibitory concentrations(MICs) of 12.25,25,12.5,12.5,6.25 and 6.25 mg/L against B.subtilis, S.aureus, S.faecalis, P.aeruginosa, E.coli and E.cloacae, respectively.
5-Chlorosalicylaldehyde-2-aminoethanol-copper(Ⅱ) was synthesized using 5-chlorosalicylaldehyde,2-aminoethanol and cupric chloride as precursors under microwave irradiation. The product was characterized by IR spectra,elemental analysis and single X-ray crystallography study. The title complex crystallizes in the monoclinic space group P21/n. Cell parameters:a=0.49793(6) nm,b=1.7037(2) nm,c=1.07120(12) nm,β=94.579(3)°,F(000)=470,Z=2,V=0.905(8) nm3,Dc=1.689 mg/m3,R[I>2σ(I)],R1=0.0624,ωR2=0.1555. The Cu(Ⅱ) adopts a square planar configuration coordinated by two nitrogen atoms and two oxygen atoms from two Schiff bases. The antibacterial (B.subtilis, S.aureus, S.faecalis, P.aeruginosa, E.coli and E.cloacae) activities of the compounds were assayed by MTT (3-(4,5-dimethylthiazol-2-yl) -2,5-diphenyl tetrazolium bromide) method. It showed favorable antimicrobial activity with minimal inhibitory concentrations(MICs) of 12.25,25,12.5,12.5,6.25 and 6.25 mg/L against B.subtilis, S.aureus, S.faecalis, P.aeruginosa, E.coli and E.cloacae, respectively.
2013, 30(3): 300-304
doi: 10.3724/SP.J.1095.2013.20190
Abstract:
A novel fluorescent calix[4] arene derivative(1) bonded with coumarin units as fluorophores and imino groups as ionophores was synthesized by condensation of 5,17-diaminocalix[4] arene with 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde. The structure of compound 1 was fully characterized by IR,1H NMR,13C NMR and MS. The recognition properties of compound 1 toward transition and heavy metal ions were studied by UV-Vis and fluorescent spectroscopies. The results show that compound 1 can selectively recognize Fe3+ and Cr3+ ions. The complexation ratio of compound 1 with Fe3+or Cr3+ is 1:1. The association constants of compound 1 with Fe3+ and Cr3+ were 4.1 × 105 and 1.07 × 105 L/mol,respectively.
A novel fluorescent calix[4] arene derivative(1) bonded with coumarin units as fluorophores and imino groups as ionophores was synthesized by condensation of 5,17-diaminocalix[4] arene with 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde. The structure of compound 1 was fully characterized by IR,1H NMR,13C NMR and MS. The recognition properties of compound 1 toward transition and heavy metal ions were studied by UV-Vis and fluorescent spectroscopies. The results show that compound 1 can selectively recognize Fe3+ and Cr3+ ions. The complexation ratio of compound 1 with Fe3+or Cr3+ is 1:1. The association constants of compound 1 with Fe3+ and Cr3+ were 4.1 × 105 and 1.07 × 105 L/mol,respectively.
2013, 30(3): 305-309
doi: 10.3724/SP.J.1095.2013.20290
Abstract:
Two complexes of[M(2,2'-bpy)2]2SiW12O40 (M=Mn(1) and M=Co(2)) have been synthesized under hydrothermal conditions and their structures were determined by using elemental analyses,IR,TG and single-crystal X-ray diffraction methods.The results showed that complexes 1 and 2 were isomorphic.The electrocatalytic activities of the two complexes toward the oxidation of H2O to O2 were preliminary evaluated.The result showed that only complex 1 has such electrocatalytic activity.
Two complexes of[M(2,2'-bpy)2]2SiW12O40 (M=Mn(1) and M=Co(2)) have been synthesized under hydrothermal conditions and their structures were determined by using elemental analyses,IR,TG and single-crystal X-ray diffraction methods.The results showed that complexes 1 and 2 were isomorphic.The electrocatalytic activities of the two complexes toward the oxidation of H2O to O2 were preliminary evaluated.The result showed that only complex 1 has such electrocatalytic activity.
2013, 30(3): 310-315
doi: 10.3724/SP.J.1095.2013.20152
Abstract:
Ionic liquid-like polyoxometalates (POM-IL),[PyPS]nH3-nPW12O40·xH2O(n=1,2,3),were synthesized by using pyridine,1,3-propanesultone and tungstophosphoric acid as raw materials. The compounds were characterized by means of FT-IR,UV-Vis,1H NMR and elementary analyses. The results showed that Keggin structure of POM was kept and there were character bands of pyridyl propylsulfonic acid in the POM-IL salts. All prepared compounds possess melting-points above 130℃ and the melting-points decreased with the increase of the organic component. Furthermore,the photocatalytic performances of these POM-IL samples for the degradation of aqueous dyes were investigated.Under UV irradiation,the samples with n=1 and 2 showed similar photocatalytic activities to that of tungstophosphoric acid for the degradation of methyl orange. Under visible light,all POM-IL salts exhibit the same photocatlytic activities which are superior to tungstophosphoric acid for the degradation of isatin.Therefore,all these POM-IL salts might be promising photocatalysts for the degradation of some dyes under visible light.
Ionic liquid-like polyoxometalates (POM-IL),[PyPS]nH3-nPW12O40·xH2O(n=1,2,3),were synthesized by using pyridine,1,3-propanesultone and tungstophosphoric acid as raw materials. The compounds were characterized by means of FT-IR,UV-Vis,1H NMR and elementary analyses. The results showed that Keggin structure of POM was kept and there were character bands of pyridyl propylsulfonic acid in the POM-IL salts. All prepared compounds possess melting-points above 130℃ and the melting-points decreased with the increase of the organic component. Furthermore,the photocatalytic performances of these POM-IL samples for the degradation of aqueous dyes were investigated.Under UV irradiation,the samples with n=1 and 2 showed similar photocatalytic activities to that of tungstophosphoric acid for the degradation of methyl orange. Under visible light,all POM-IL salts exhibit the same photocatlytic activities which are superior to tungstophosphoric acid for the degradation of isatin.Therefore,all these POM-IL salts might be promising photocatalysts for the degradation of some dyes under visible light.
2013, 30(3): 316-322
doi: 10.3724/SP.J.1095.2013.20208
Abstract:
Surface molecularly imprinted polymer(H-SiO2@MIP) based on hybrid silica microspheres was prepared by using di(2-ethylhexyl)phthalate(DIOP) as the template molecule,methacrylic acid(MAA) as the functional monomer and ethylene glycol dimethacrylate(EGDMA) as the cross-linking agent. The H-SiO2@MIP was characterized by scanning electron microscope(SEM) and infrared spectroscopy(IR). The results showed that DIOP imprinted layer was grafted on particles surface successfully. The H-SiO2@MIP has uniform spherical structure and the thickness of imprinted shell is about 60-70 nm. The adsorption properties were investigated by high performance liquid chromatography,and results demonstrated that the H-SiO2@MIP exhibited specific selectivity towards DIOP. The maximum adsorption capacity of H-SiO2@MIP was 50.35 mg/g,and the selectivity factor of DIOP towards dibutyl phthalate(DBP) and dimethyl phthalate(DEP) was 2.31 and 2.47,respectively. Packed into a solid-phase extraction(SPE) column,the H-SiO2@MIP could separate and enrich DIOP from milk sample.
Surface molecularly imprinted polymer(H-SiO2@MIP) based on hybrid silica microspheres was prepared by using di(2-ethylhexyl)phthalate(DIOP) as the template molecule,methacrylic acid(MAA) as the functional monomer and ethylene glycol dimethacrylate(EGDMA) as the cross-linking agent. The H-SiO2@MIP was characterized by scanning electron microscope(SEM) and infrared spectroscopy(IR). The results showed that DIOP imprinted layer was grafted on particles surface successfully. The H-SiO2@MIP has uniform spherical structure and the thickness of imprinted shell is about 60-70 nm. The adsorption properties were investigated by high performance liquid chromatography,and results demonstrated that the H-SiO2@MIP exhibited specific selectivity towards DIOP. The maximum adsorption capacity of H-SiO2@MIP was 50.35 mg/g,and the selectivity factor of DIOP towards dibutyl phthalate(DBP) and dimethyl phthalate(DEP) was 2.31 and 2.47,respectively. Packed into a solid-phase extraction(SPE) column,the H-SiO2@MIP could separate and enrich DIOP from milk sample.
2013, 30(3): 323-328
doi: 10.3724/SP.J.1095.2013.20169
Abstract:
A new method for the determination of pentachlorophenol(PCP) in human urine has been developed by headspace solid-phase microextraction with gas chromatography(HS-SPME-GC).A homemade ionic liquid(IL) bonded coating solid-phase microextraction was added by the sol-gel method.The extraction conditions were optimized as the extraction temperature of 80℃,extraction time of 50 min by headspace,desorption time of 5 min at 300℃,NaCl amount of 3 g,pH of 2 and under stirring.The detection limits was 5.0 ng/L.The linear range was 0.05-100 μg/L.The relative standard deviations(RSD) was 5.9%.The recovery was 106.6%.
A new method for the determination of pentachlorophenol(PCP) in human urine has been developed by headspace solid-phase microextraction with gas chromatography(HS-SPME-GC).A homemade ionic liquid(IL) bonded coating solid-phase microextraction was added by the sol-gel method.The extraction conditions were optimized as the extraction temperature of 80℃,extraction time of 50 min by headspace,desorption time of 5 min at 300℃,NaCl amount of 3 g,pH of 2 and under stirring.The detection limits was 5.0 ng/L.The linear range was 0.05-100 μg/L.The relative standard deviations(RSD) was 5.9%.The recovery was 106.6%.
2013, 30(3): 329-334
doi: 10.3724/SP.J.1095.2013.20174
Abstract:
Spectral correlative chromatography was used to identify the peak of tetrahydropalmatine in Corydalis yanhusuo fingerprint. Moreover, multivariate curve resolution-alternating least squares(MCR-ALS) was used to resolve the overlapping peaks of tetrahydropalmatine and restore its true peak shape. More than 99.9% spectrum could be recovered and accurately quantitative results were obtained. The method can be used as an auxillary fingerprinting method to provide a reliable basis for the authenticity and quality assessment of Chinese medicines. The effect of the herbs-cooking on the content of tetrahydropalmatine was also discussed.
Spectral correlative chromatography was used to identify the peak of tetrahydropalmatine in Corydalis yanhusuo fingerprint. Moreover, multivariate curve resolution-alternating least squares(MCR-ALS) was used to resolve the overlapping peaks of tetrahydropalmatine and restore its true peak shape. More than 99.9% spectrum could be recovered and accurately quantitative results were obtained. The method can be used as an auxillary fingerprinting method to provide a reliable basis for the authenticity and quality assessment of Chinese medicines. The effect of the herbs-cooking on the content of tetrahydropalmatine was also discussed.
2013, 30(3): 335-342
doi: 10.3724/SP.J.1095.2013.20206
Abstract:
In an acid solution,an isopoly-acid anion such as isopoly-molybdic acid or isopoly-tungstic acid could react with prazosin hydrochloride(PRH) and doxazosin mesyllate(Dox) α1-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of resonance Rayleigh scattering(RRS) intensities and new RRS peaks. The maximum RRS wavelength was located at 367 nm for isopoly-molybdic acid system and 290 nm for isopoly-tungstic acid system. The reaction products of the two drugs had similar spectral characteristics.The optimum pH ranges were 2.1-2.3 for isopoly-molybdic acid-PRH system and 3.1-3.3 for isopoly-tungstic acid-PRH system.In a certain range,the intensities of RRS were directly proportional to the concentration of drugs for the two different reaction systems.The reactions exhibited a high sensitivity,with a detection limit(3σ/s) of 4.76 μg/L (isopoly-molybdic acid-PRH system) and 9.88 μg/L (isopoly-tungstic acid-PRH system) for PRH,and also showed a good selectivity. The method was applied to the determination of α1-receptor blocker drugs in tablets and human urine samples. Density functional theory(DFT) calculations with Gaussian 03W at B3LYP/6-31G level were performed to calculate the charge distribution of PRH for investigating the reaction mechanism; in addition,the reasons for the RRS enhancement of the system were discussed.
In an acid solution,an isopoly-acid anion such as isopoly-molybdic acid or isopoly-tungstic acid could react with prazosin hydrochloride(PRH) and doxazosin mesyllate(Dox) α1-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of resonance Rayleigh scattering(RRS) intensities and new RRS peaks. The maximum RRS wavelength was located at 367 nm for isopoly-molybdic acid system and 290 nm for isopoly-tungstic acid system. The reaction products of the two drugs had similar spectral characteristics.The optimum pH ranges were 2.1-2.3 for isopoly-molybdic acid-PRH system and 3.1-3.3 for isopoly-tungstic acid-PRH system.In a certain range,the intensities of RRS were directly proportional to the concentration of drugs for the two different reaction systems.The reactions exhibited a high sensitivity,with a detection limit(3σ/s) of 4.76 μg/L (isopoly-molybdic acid-PRH system) and 9.88 μg/L (isopoly-tungstic acid-PRH system) for PRH,and also showed a good selectivity. The method was applied to the determination of α1-receptor blocker drugs in tablets and human urine samples. Density functional theory(DFT) calculations with Gaussian 03W at B3LYP/6-31G level were performed to calculate the charge distribution of PRH for investigating the reaction mechanism; in addition,the reasons for the RRS enhancement of the system were discussed.
2013, 30(3): 343-348
doi: 10.3724/SP.J.1095.2013.20109
Abstract:
Different self-assembled thiol-substituted porphyrin monolayers (TPPS1 and TPPS4) were prepared and characterized by means of UV-Vis,CV,EIS and XPS.The results showed that the self-assembled porphyrin monolayers have different configurations due to the different numbers of the thiol-substitute in porphyrin molecules.Therefore,these porphyrin monolayers showed different performance in catalysis.On the basis of those observations,we proposed a model for the assembling of multi-thiol substituted porphyrin into monolayer.The established method shows potential for building and developing functional self-assembled porphyrin monolayers in the application of bio-catalysis and optoelectronic devices.
Different self-assembled thiol-substituted porphyrin monolayers (TPPS1 and TPPS4) were prepared and characterized by means of UV-Vis,CV,EIS and XPS.The results showed that the self-assembled porphyrin monolayers have different configurations due to the different numbers of the thiol-substitute in porphyrin molecules.Therefore,these porphyrin monolayers showed different performance in catalysis.On the basis of those observations,we proposed a model for the assembling of multi-thiol substituted porphyrin into monolayer.The established method shows potential for building and developing functional self-assembled porphyrin monolayers in the application of bio-catalysis and optoelectronic devices.
2013, 30(3): 349-353
doi: 10.3724/SP.J.1095.2013.20215
Abstract:
A new Schiff base was synthesized from ethylenediamine and acetylacetone using hydrochloric acid as catalyst. The yield of the target base was about 73.2%. 1H NMR and FT-IR were performed to determine the structure of the final product. Polarization curves, electrochemical impedance and the corrosion potential-time curves of the Schiff base self-assembled membranes on stainless steel(SS/SAMs) were analyzed. The result showed that,in 1.0 mol/L HCl,the SS/SAMs can effectively inhibit the heterogeneous electron transfer,promote the stainless steel surface passivation,and reduce corrosion of the stainless steel substrate. Effectiveness and value of metal protection of Schiff base were summarized.
A new Schiff base was synthesized from ethylenediamine and acetylacetone using hydrochloric acid as catalyst. The yield of the target base was about 73.2%. 1H NMR and FT-IR were performed to determine the structure of the final product. Polarization curves, electrochemical impedance and the corrosion potential-time curves of the Schiff base self-assembled membranes on stainless steel(SS/SAMs) were analyzed. The result showed that,in 1.0 mol/L HCl,the SS/SAMs can effectively inhibit the heterogeneous electron transfer,promote the stainless steel surface passivation,and reduce corrosion of the stainless steel substrate. Effectiveness and value of metal protection of Schiff base were summarized.
2013, 30(3): 354-359
doi: 10.3724/SP.J.1095.2013.20205
Abstract:
Carboxyl graphene-based polypyrrole(CG/ppy) modified electrode was prepared and its electrochemical properties were investigated via cyclic voltammetry and AC impedance.Additionally,galvanostatic charge-discharge tests and cycle stability tests were performed.Experimental results show that the CG/ppy significantly improves the current response of the bare electrode and reduces the resistance of the bare electrode in the supporting electrolyte.The specific capacitance of the CG/ppy modified electrode is up to 584 F/g and retains 81% of the initial value after 1000 cycles.Therefore CG/ppy modified electrode has potential application value in the field of electrochemical area.
Carboxyl graphene-based polypyrrole(CG/ppy) modified electrode was prepared and its electrochemical properties were investigated via cyclic voltammetry and AC impedance.Additionally,galvanostatic charge-discharge tests and cycle stability tests were performed.Experimental results show that the CG/ppy significantly improves the current response of the bare electrode and reduces the resistance of the bare electrode in the supporting electrolyte.The specific capacitance of the CG/ppy modified electrode is up to 584 F/g and retains 81% of the initial value after 1000 cycles.Therefore CG/ppy modified electrode has potential application value in the field of electrochemical area.
2013, 30(3): 360-366
doi: 10.3724/SP.J.1095.2013.20257
Abstract:
The method of preparing novel poly N,N-dimethyl aniline(PDMA)/multi-walled carbon nanotubes(MWNT) composite film modified glassy carbon(GC) electrode was investigated.SEM and electrochemical characterizations indicated that the morphology and electrochemical performance of the PDMA film were changed no matter the MWNT was doped or drop coated to DMA.The composite film modified electrode greatly increased the specific surface area and the electrical activation area compared with a single PDMA film modified electrode,indicating that the PDMA and MWNT play important roles in improving the electrochemical properties.The results showed that the electrochemical response of vanillin is much greater on the PDMA/MWNT/GC layers than on the bare GC electrode and other modified electrodes.The over potential was reduced by 148 mV,and the oxidation peak current was increased by about six times.The electrode reaction was an irreversible redox process and was likely an adsorptive process.The numbers of the electron and proton transferred in the electrode reaction were 2 and 1,respectively,the transfer coefficient was calculated to be 0.4062,and the amount of adsorption was 3.527 × 10-9 mol/cm2.The detection limit was 8.0 × 10-7 mol/L,and the average recovery was 99.87%.
The method of preparing novel poly N,N-dimethyl aniline(PDMA)/multi-walled carbon nanotubes(MWNT) composite film modified glassy carbon(GC) electrode was investigated.SEM and electrochemical characterizations indicated that the morphology and electrochemical performance of the PDMA film were changed no matter the MWNT was doped or drop coated to DMA.The composite film modified electrode greatly increased the specific surface area and the electrical activation area compared with a single PDMA film modified electrode,indicating that the PDMA and MWNT play important roles in improving the electrochemical properties.The results showed that the electrochemical response of vanillin is much greater on the PDMA/MWNT/GC layers than on the bare GC electrode and other modified electrodes.The over potential was reduced by 148 mV,and the oxidation peak current was increased by about six times.The electrode reaction was an irreversible redox process and was likely an adsorptive process.The numbers of the electron and proton transferred in the electrode reaction were 2 and 1,respectively,the transfer coefficient was calculated to be 0.4062,and the amount of adsorption was 3.527 × 10-9 mol/cm2.The detection limit was 8.0 × 10-7 mol/L,and the average recovery was 99.87%.
