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2010 Volume 27 Issue 6
2010, 27(6): 612-625
doi: 10.3724/SP.J.1095.2010.90424
Abstract:
The research progress on oxidative bromination reactions of compounds with functional groups including α-carbonyl hydrogen, the ring of arene, alkene double bond,the side chain of arene and alkanes is reviewed. The main oxidation of bromide system is Br-/H2O2 and Br-/BrO3-. The different conditions of reaction are discussed in detail. The perspective on this research field is also suggested.
The research progress on oxidative bromination reactions of compounds with functional groups including α-carbonyl hydrogen, the ring of arene, alkene double bond,the side chain of arene and alkanes is reviewed. The main oxidation of bromide system is Br-/H2O2 and Br-/BrO3-. The different conditions of reaction are discussed in detail. The perspective on this research field is also suggested.
2010, 27(6): 626-631
doi: 10.3724/SP.J.1095.2010.90592
Abstract:
The synthesis of copolymer with high comonomer incorporation and broadened molecular mass distribution from ethylene with 1-hexene catalyzed by co-catalyst TiCl4/XROH/MgCl2 and Et3Al is described.The influences of the catalyst system composition and the polymerization conditions on the behavior of ethylene/1-hexene copolymerization,the structure,molecular mass and molecular mass distribution(MMD) of the obtained copolymer have been discussed in detail. When the copolymerization was performed under the optimum conditions:n(Ti):n(Mg)=10:1, n(XROH):n(MgCl2)=2.6:1, n(Al):n(Ti)=100:1, P=0.45 MPa, t=80℃, Time=2 h and the comonomer concentration in feed=0.25 mol/L,the catalytic activity reached 23.2 kg/g cat. The catalyst particle shape and the structure and properties of the ethylene/1-octene copolymer are characterized with 13C NMR, X-ray, SEM,WAXD,DSC and GPC. These results show that the catalytic activity, molecular mass distribution and higher 1-hexene incorporation were considerably improved when the multi-halogen alcohol(XROH) was added into the catalyst system. By adding XROH in the catalyst system made Ti mass fraction of the catalyst increased up to 4.8%; the molar ratio of MMD of the copolymer became broader,ranging from 15 to 20;1-hexene incorporation within the copolymer chain was higher, up to 5.1%.
The synthesis of copolymer with high comonomer incorporation and broadened molecular mass distribution from ethylene with 1-hexene catalyzed by co-catalyst TiCl4/XROH/MgCl2 and Et3Al is described.The influences of the catalyst system composition and the polymerization conditions on the behavior of ethylene/1-hexene copolymerization,the structure,molecular mass and molecular mass distribution(MMD) of the obtained copolymer have been discussed in detail. When the copolymerization was performed under the optimum conditions:n(Ti):n(Mg)=10:1, n(XROH):n(MgCl2)=2.6:1, n(Al):n(Ti)=100:1, P=0.45 MPa, t=80℃, Time=2 h and the comonomer concentration in feed=0.25 mol/L,the catalytic activity reached 23.2 kg/g cat. The catalyst particle shape and the structure and properties of the ethylene/1-octene copolymer are characterized with 13C NMR, X-ray, SEM,WAXD,DSC and GPC. These results show that the catalytic activity, molecular mass distribution and higher 1-hexene incorporation were considerably improved when the multi-halogen alcohol(XROH) was added into the catalyst system. By adding XROH in the catalyst system made Ti mass fraction of the catalyst increased up to 4.8%; the molar ratio of MMD of the copolymer became broader,ranging from 15 to 20;1-hexene incorporation within the copolymer chain was higher, up to 5.1%.
2010, 27(6): 632-636
doi: 10.3724/SP.J.1095.2010.90544
Abstract:
A fluorescent chemosensor,N'-((2-hydroxynaphthalen-1-yl)methylene)-2-naphthohydrazone(3), was designed and synthesized. Compound 3 was confirmed by IR,1H NMR and ESI-MS. Compound 3 was investigated to recognize transition metal ions such as Zn2+, Cd2+, Cu2+, Hg2+, Pb2+ and Ni2+ via the fluorescence spectroscopic method. Mechanism of enhancement of the fluorescence of compound 3 by Zn2+ was briefly discussed. The experiments show that acceptor 3 has a good selectivity of Zn2+ in acetonitrile. A new peak in the absorption spectrum of acceptor 3 at 435 nm appears for the addition of Zn2+ with the gradually increasing absorbancy,while five clear absorption points can be observed at 239, 302, 330, 342 and 387 nm, respectively. The fluorescence of acceptor 3 shows a highly selective response to Zn2+ only. In acetonitrile Zn2+ induced a dramatic enhancement in the fluorescence of acceptor 3 by 101 folds at 516 nm, whereas the other transition metal ions had little influence on the fluorescence of acceptor 3. Job's test showed acceptor 3 coordinated to Zn2+ to form a 1:1 model complex.
A fluorescent chemosensor,N'-((2-hydroxynaphthalen-1-yl)methylene)-2-naphthohydrazone(3), was designed and synthesized. Compound 3 was confirmed by IR,1H NMR and ESI-MS. Compound 3 was investigated to recognize transition metal ions such as Zn2+, Cd2+, Cu2+, Hg2+, Pb2+ and Ni2+ via the fluorescence spectroscopic method. Mechanism of enhancement of the fluorescence of compound 3 by Zn2+ was briefly discussed. The experiments show that acceptor 3 has a good selectivity of Zn2+ in acetonitrile. A new peak in the absorption spectrum of acceptor 3 at 435 nm appears for the addition of Zn2+ with the gradually increasing absorbancy,while five clear absorption points can be observed at 239, 302, 330, 342 and 387 nm, respectively. The fluorescence of acceptor 3 shows a highly selective response to Zn2+ only. In acetonitrile Zn2+ induced a dramatic enhancement in the fluorescence of acceptor 3 by 101 folds at 516 nm, whereas the other transition metal ions had little influence on the fluorescence of acceptor 3. Job's test showed acceptor 3 coordinated to Zn2+ to form a 1:1 model complex.
2010, 27(6): 637-641
doi: 10.3724/SP.J.1095.2010.90504
Abstract:
Temperature-sensitive hydrogels P(NIPA-co-DiAB) with aromatic group as hydrophobe was were prepared by free radical micellar crosslinking copolymerization with N-isopropyl acrylamide(NIPA) and N,N-dially benzylamine(DiAB) as comonomers,N,N-methylene-bis-acrylamide(BIS) as crosslinker,sodium dodecyl sulfate(SDS) as surfactant and ammonium persulfate(APS)-tetramethylethylenediamine(TMEDA) as initiator system.The influence of DiAB content on the properties of the hydrogels was discussed.In the initial swelling stage,the swelling behavior of the four hydrogels changed from Fickian kinetics to non-Fickian with increasing of molar fraction x(DiAB) from 0 to 3%.While x(DiAB) values were 0,1%,2% and 3%,the equilibrium swelling ratio SR0 of P(NIPA-co-DiAB) hydrogels were 63.6,93.5,141.6 and 167.4 in distilled water;63.1,71.0,59.0 and 77.5 in a 0.01 mol/L SDS solution;37.6,42.2,44.1 and 60.0 in a 0.01mol/L CTAB solution;30.9,49.4,68.5 and 88.3 in a 0.01 mol/L Triton X-100 solution respectively.It was found that the SR0 values of P(NIPA-co-DiAB) hydrogels were greater than that of PNIPA,and the SR0 values of the four hydrogels in distilled water were greater than those in 0.01 mol/L aqueous surfactant solution.The volume phase transition temperature or lower critical swelling temperature(LCST) of PNIPA hydrogel was enhanced from 32.5℃ in distilled water to 35.4℃,45.6℃ or 80℃ in a 0.01 mol/L Triton X-100,CTAB or SDS solution,respectively.The LCST of P(NIPA-co-DiAB) hydrogels was increased from 32.0~32.5℃ in distilled water to 34.7~35.6℃,about 45.8~46.2℃ or 80℃ in a 0.01 mol/L Triton X-100,CTAB or SDS solution,respectively.It was shown that the LCST of P(NIPA-co-DiAB) hydrogels was increased by adding surfactant.The high volume transition temperature was essentially independent of hydrophobic comonomer DiAB content.
Temperature-sensitive hydrogels P(NIPA-co-DiAB) with aromatic group as hydrophobe was were prepared by free radical micellar crosslinking copolymerization with N-isopropyl acrylamide(NIPA) and N,N-dially benzylamine(DiAB) as comonomers,N,N-methylene-bis-acrylamide(BIS) as crosslinker,sodium dodecyl sulfate(SDS) as surfactant and ammonium persulfate(APS)-tetramethylethylenediamine(TMEDA) as initiator system.The influence of DiAB content on the properties of the hydrogels was discussed.In the initial swelling stage,the swelling behavior of the four hydrogels changed from Fickian kinetics to non-Fickian with increasing of molar fraction x(DiAB) from 0 to 3%.While x(DiAB) values were 0,1%,2% and 3%,the equilibrium swelling ratio SR0 of P(NIPA-co-DiAB) hydrogels were 63.6,93.5,141.6 and 167.4 in distilled water;63.1,71.0,59.0 and 77.5 in a 0.01 mol/L SDS solution;37.6,42.2,44.1 and 60.0 in a 0.01mol/L CTAB solution;30.9,49.4,68.5 and 88.3 in a 0.01 mol/L Triton X-100 solution respectively.It was found that the SR0 values of P(NIPA-co-DiAB) hydrogels were greater than that of PNIPA,and the SR0 values of the four hydrogels in distilled water were greater than those in 0.01 mol/L aqueous surfactant solution.The volume phase transition temperature or lower critical swelling temperature(LCST) of PNIPA hydrogel was enhanced from 32.5℃ in distilled water to 35.4℃,45.6℃ or 80℃ in a 0.01 mol/L Triton X-100,CTAB or SDS solution,respectively.The LCST of P(NIPA-co-DiAB) hydrogels was increased from 32.0~32.5℃ in distilled water to 34.7~35.6℃,about 45.8~46.2℃ or 80℃ in a 0.01 mol/L Triton X-100,CTAB or SDS solution,respectively.It was shown that the LCST of P(NIPA-co-DiAB) hydrogels was increased by adding surfactant.The high volume transition temperature was essentially independent of hydrophobic comonomer DiAB content.
2010, 27(6): 642-645
doi: 10.3724/SP.J.1095.2010.90531
Abstract:
In the ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate,atom transfer radical polymerization of acrylamide(AM) was completed with benzyl chloride as the initiator and cuprous chloride/2,2'-bipyridine as catalyst.The structural analysis of the resulting polymer via IR spectrometry demonstrates its terminal has -Cl end group.The effects of initiator amount,monomer amount and reaction time on the ATRP of AM are studied,and the results show that when the reaction time is 1.5 h,the conversion is 31.43%, MnGPC=4451 and Mw/Mn=1.38 in ionic liquid at 80℃. The best conditions of polymerization are as follows:the monomer concentration is 3 mol/L,the initiator concentration is 0.010 mol/L,the catalyst concentration is 0.015 mol/L,and the rection time is 1 h.
In the ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate,atom transfer radical polymerization of acrylamide(AM) was completed with benzyl chloride as the initiator and cuprous chloride/2,2'-bipyridine as catalyst.The structural analysis of the resulting polymer via IR spectrometry demonstrates its terminal has -Cl end group.The effects of initiator amount,monomer amount and reaction time on the ATRP of AM are studied,and the results show that when the reaction time is 1.5 h,the conversion is 31.43%, MnGPC=4451 and Mw/Mn=1.38 in ionic liquid at 80℃. The best conditions of polymerization are as follows:the monomer concentration is 3 mol/L,the initiator concentration is 0.010 mol/L,the catalyst concentration is 0.015 mol/L,and the rection time is 1 h.
2010, 27(6): 646-650
doi: 10.3724/SP.J.1095.2010.90497
Abstract:
Ethyl 3-(4-methoxy phenyl)-1H-pyrazole-5-carboxylate was synthesized by means of one-pot reaction method;and two kinds of pyrazole carboxylic acid were obtained through methylation at position 1,chlorination at position 4 and hydrolysis.Six 5-substituted-2-amino-1,3,4-thiadiazoles were obtained from substituted carboxylic acids and thiosemicarbazide using phosphorus acylchloride as the dehydrating agent.Pyrazole and 1,3,4-thiadiazole were connected together by amido bond and 12 new compounds were synthesized.The yield of the title compounds was up to 50%.All the new compounds were confirmed by means of elemental analysis,IR and 1H NMR spectroscopies.Their auxin activities are not high,and a few of them are antiblastic to wheat gemma.
Ethyl 3-(4-methoxy phenyl)-1H-pyrazole-5-carboxylate was synthesized by means of one-pot reaction method;and two kinds of pyrazole carboxylic acid were obtained through methylation at position 1,chlorination at position 4 and hydrolysis.Six 5-substituted-2-amino-1,3,4-thiadiazoles were obtained from substituted carboxylic acids and thiosemicarbazide using phosphorus acylchloride as the dehydrating agent.Pyrazole and 1,3,4-thiadiazole were connected together by amido bond and 12 new compounds were synthesized.The yield of the title compounds was up to 50%.All the new compounds were confirmed by means of elemental analysis,IR and 1H NMR spectroscopies.Their auxin activities are not high,and a few of them are antiblastic to wheat gemma.
2010, 27(6): 651-657
doi: 10.3724/SP.J.1095.2010.90513
Abstract:
Fourteen new 3-substituted-6-(4'-decarboxydehydroabietyl)-1,2,4-triazolo-[3,4-b]-1,3,4-thiadiazoles 5a~5e and 11a~11i were obtained from the reaction of 3-substituted-4-amino-5-mercapto-1,2,4-triazoles 4 and 10 with dehydroabietic acid 1 in the presence of phosphorus oxychloride,respectively.All target compounds were characterized by IR,1H NMR,13C NMR and MS.The preliminary antibacterial activity assay showed that title compounds 5 and 11 exhibited a fungicidal activity against C.Albicans, E.coli., M.Luteus and S.Dysenteriae.
Fourteen new 3-substituted-6-(4'-decarboxydehydroabietyl)-1,2,4-triazolo-[3,4-b]-1,3,4-thiadiazoles 5a~5e and 11a~11i were obtained from the reaction of 3-substituted-4-amino-5-mercapto-1,2,4-triazoles 4 and 10 with dehydroabietic acid 1 in the presence of phosphorus oxychloride,respectively.All target compounds were characterized by IR,1H NMR,13C NMR and MS.The preliminary antibacterial activity assay showed that title compounds 5 and 11 exhibited a fungicidal activity against C.Albicans, E.coli., M.Luteus and S.Dysenteriae.
2010, 27(6): 658-663
doi: 10.3724/SP.J.1095.2010.90532
Abstract:
2,6-Di(2'-imidazoline-2'-yl)pyridine,even though it is not fully aromatic,has the same distribution of heteroatoms as 2,6-di(2'-benzimidazol-2'-yl)pyridine and has been synthesized from pyridine 2,6-dicarboxylic acid and ethylenediamine under microwave irradiation and without catalyst. The composition and structure of the product were identified and characterized by IR,mass spectrometry,1H NMR,13C NMR and melting point determination. The ratio of products and by-product was found to be different under different experimental conditions(solvents,proportion of reacting mass,power of microwave irradiation). Among them,solvents have very obvious effects on the ratio of product and by-product. The experimental results indicate that the best solvent is ethylene glycol. The optimal reaction condition are follows:molar ratio of raw materials 1:2.7,microwave power 450 W,irradiation time 65 min,irradiation temperature 130℃ and the overall yield 71.2%.The binding of this compound with calf thymus DNA was investigated by UV and viscosity measurements.The binding constant Kb is meaused to be(9.60±0.05)×104 L/mol,which is lower than those observed for typical classical intercalators.The results of viscosity measurement reveal that the presence of 2,6-di(2'-imidazoline-2'-yl)pyridine has no obvious effect on the relative viscosity of DNA.It may bind to DNA by hydrogen bonding and groove-face binding.
2,6-Di(2'-imidazoline-2'-yl)pyridine,even though it is not fully aromatic,has the same distribution of heteroatoms as 2,6-di(2'-benzimidazol-2'-yl)pyridine and has been synthesized from pyridine 2,6-dicarboxylic acid and ethylenediamine under microwave irradiation and without catalyst. The composition and structure of the product were identified and characterized by IR,mass spectrometry,1H NMR,13C NMR and melting point determination. The ratio of products and by-product was found to be different under different experimental conditions(solvents,proportion of reacting mass,power of microwave irradiation). Among them,solvents have very obvious effects on the ratio of product and by-product. The experimental results indicate that the best solvent is ethylene glycol. The optimal reaction condition are follows:molar ratio of raw materials 1:2.7,microwave power 450 W,irradiation time 65 min,irradiation temperature 130℃ and the overall yield 71.2%.The binding of this compound with calf thymus DNA was investigated by UV and viscosity measurements.The binding constant Kb is meaused to be(9.60±0.05)×104 L/mol,which is lower than those observed for typical classical intercalators.The results of viscosity measurement reveal that the presence of 2,6-di(2'-imidazoline-2'-yl)pyridine has no obvious effect on the relative viscosity of DNA.It may bind to DNA by hydrogen bonding and groove-face binding.
2010, 27(6): 664-668
doi: 10.3724/SP.J.1095.2010.90541
Abstract:
Twelve new 5-benzyl-4-tert-butyl-2-benzyliminothiazoles were synthesized via the reacitions of 5-benzyl-4-tert-butylthiazol-2-amines with salicyladehyde derivatives. The bioassay of twenty five 4-tert-butyl-5-benzyl-2-benzyliminothiazoles were made. The results of preliminary bioassay show that the inhibition rate of compound 1a(500 mg/L) is 95% against R.solani;the inhibition rates of compounds 1i,1j,1l,1p,1q and 1s(25 mg/L) are 55.1%,55.1%,51.3%,51.5%,51.5% and 51.5% against G.zeae respectively;the inhibition rates of compounds 1i,1l and 1s are 51.1%,51.9% and 64.9% against P.capsici; the inhibition rates of compounds 1h and 1j (25 mg/L) are 53.1% and 61.2% against B.cinerea respectively; the inhibition rates of compounds 1t,1o and 1r(25 mg/L) are 56.1%,56.1% and 65.4% against S.sclerotiorum respectively;and the inhibition rate of compound 1w(25 mg/L) is 52.6% against A.alternata.
Twelve new 5-benzyl-4-tert-butyl-2-benzyliminothiazoles were synthesized via the reacitions of 5-benzyl-4-tert-butylthiazol-2-amines with salicyladehyde derivatives. The bioassay of twenty five 4-tert-butyl-5-benzyl-2-benzyliminothiazoles were made. The results of preliminary bioassay show that the inhibition rate of compound 1a(500 mg/L) is 95% against R.solani;the inhibition rates of compounds 1i,1j,1l,1p,1q and 1s(25 mg/L) are 55.1%,55.1%,51.3%,51.5%,51.5% and 51.5% against G.zeae respectively;the inhibition rates of compounds 1i,1l and 1s are 51.1%,51.9% and 64.9% against P.capsici; the inhibition rates of compounds 1h and 1j (25 mg/L) are 53.1% and 61.2% against B.cinerea respectively; the inhibition rates of compounds 1t,1o and 1r(25 mg/L) are 56.1%,56.1% and 65.4% against S.sclerotiorum respectively;and the inhibition rate of compound 1w(25 mg/L) is 52.6% against A.alternata.
2010, 27(6): 669-672
doi: 10.3724/SP.J.1095.2010.90530
Abstract:
An efficient method for the synthesis of fluoroaromatics with tetramethylammonium fluoride(TMAFanh.) as fluorination agent via the fluorodenitration reaction was reported.Fluoroaromatics were obtained from TMAFanh. and nitroaromatics by simply stirring them together at 80~100℃ for 1~5 h in an anhydrous solution of DMF in 19.4%~99.0% yields.The nucleophilic fluorinating method has the advantages of mild reaction conditions,high yields,easy work-up and no phenol or ether side-products were detected in the reaction.
An efficient method for the synthesis of fluoroaromatics with tetramethylammonium fluoride(TMAFanh.) as fluorination agent via the fluorodenitration reaction was reported.Fluoroaromatics were obtained from TMAFanh. and nitroaromatics by simply stirring them together at 80~100℃ for 1~5 h in an anhydrous solution of DMF in 19.4%~99.0% yields.The nucleophilic fluorinating method has the advantages of mild reaction conditions,high yields,easy work-up and no phenol or ether side-products were detected in the reaction.
2010, 27(6): 673-676
doi: 10.3724/SP.J.1095.2010.90533
Abstract:
Nine 7-amino-6-cyano-5-aryl-5H-pyrano[2,3-d] pyrimidine-2,4(1H,3H)-diones were synthesized via the one-pot three-component condensation reactions of aromatic aldehydes,malononitrile and barbituric acid in aqueous media without catalyst under the irradiation of microwave. The reactants were mixed in an equal molar ratio,and exposed to MW irradiation for 5~15 min,and the yields were 80%~92%. This method avoided the long reaction time of usual synthesis route and the troubles of isolation the intermediate and minimized the environmental pollution. The structures of the products were characterized by IR,1H NMR spectroscopies and elemental analysis.
Nine 7-amino-6-cyano-5-aryl-5H-pyrano[2,3-d] pyrimidine-2,4(1H,3H)-diones were synthesized via the one-pot three-component condensation reactions of aromatic aldehydes,malononitrile and barbituric acid in aqueous media without catalyst under the irradiation of microwave. The reactants were mixed in an equal molar ratio,and exposed to MW irradiation for 5~15 min,and the yields were 80%~92%. This method avoided the long reaction time of usual synthesis route and the troubles of isolation the intermediate and minimized the environmental pollution. The structures of the products were characterized by IR,1H NMR spectroscopies and elemental analysis.
2010, 27(6): 677-683
doi: 10.3724/SP.J.1095.2010.90537
Abstract:
A new functional monomeric complex of oxovanadium(Ⅳ),VO(imidazole)4(SO4)·H2O(1) was synthesized from the reaction of VOSO4·nH2O with imidazole in methanol at room temperature. The complex was characterized by elemental analysis,IR spectrometry and single crystal X-ray diffraction. Structure analysis reveals that complex 1 crystallized in an orthorclinic system with space group Pna21,a=1.3844(3) nm,b=0.9786(2) nm, c=1.3617(3) nm,α=β=γ=90°,V=1.8447(6) nm3,Z=4. Bromination reaction activity of the complex was evaluated by the method with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer. The reaction rate constant(k) for complex 1 was calculated as 2.7600 × 107L2/(mol2·s). The electronic structure and the bonding characters of the complex were analyzed with ab initio calculation. The atomic net charge distribution in the molecular system indicates obvious covalent interaction between the coordinating atoms and vanadium,the bond order of V-O1(1.0553) is obviously larger than that of V-O2(0.3942),the bond order of the four V-N bonds(0.3336~0.3419) is similar. The results are consistent with the structure analysis of the complex.
A new functional monomeric complex of oxovanadium(Ⅳ),VO(imidazole)4(SO4)·H2O(1) was synthesized from the reaction of VOSO4·nH2O with imidazole in methanol at room temperature. The complex was characterized by elemental analysis,IR spectrometry and single crystal X-ray diffraction. Structure analysis reveals that complex 1 crystallized in an orthorclinic system with space group Pna21,a=1.3844(3) nm,b=0.9786(2) nm, c=1.3617(3) nm,α=β=γ=90°,V=1.8447(6) nm3,Z=4. Bromination reaction activity of the complex was evaluated by the method with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer. The reaction rate constant(k) for complex 1 was calculated as 2.7600 × 107L2/(mol2·s). The electronic structure and the bonding characters of the complex were analyzed with ab initio calculation. The atomic net charge distribution in the molecular system indicates obvious covalent interaction between the coordinating atoms and vanadium,the bond order of V-O1(1.0553) is obviously larger than that of V-O2(0.3942),the bond order of the four V-N bonds(0.3336~0.3419) is similar. The results are consistent with the structure analysis of the complex.
2010, 27(6): 684-690
doi: 10.3724/SP.J.1095.2010.90461
Abstract:
Three meso-tetrakis(4-n-acyloxylphenyl) porphyrins and their platinum(Ⅱ) complexes were synthesized.The structures of the compounds and photophysical properties were characterized by 1H NMR,MS,UV-Vis and photoluminescence(PL) spectroscopies.Differential scanning calorimetry(DSC) and polarizing microscope were used to probe liquid properties of the complexes.Strong triplet emission peaks at around 660 nm were observed with phosphorescence quantum efficiencies(0.183~0.211) in THF solution and triplet lifetime(8.86~13.52 μs) in degassed CH2Cl2 solution.The results show that the attached acyloxy of the long carbon chains at the meso-positions of tetrakis(4-hydroxylphenyl) porphyrin can reduce phosphorescent lifetime and aggregation between molecules.Further,these complexes reveal characteristic of liquid crystal for long carbon chain acyloxy at the meso-positions of porphyrin complexes.It is possible that these new complexes can be used as applicable phosphorescent emitters in organic light emitter devices(OLEDs) and polarized luminescent devices.
Three meso-tetrakis(4-n-acyloxylphenyl) porphyrins and their platinum(Ⅱ) complexes were synthesized.The structures of the compounds and photophysical properties were characterized by 1H NMR,MS,UV-Vis and photoluminescence(PL) spectroscopies.Differential scanning calorimetry(DSC) and polarizing microscope were used to probe liquid properties of the complexes.Strong triplet emission peaks at around 660 nm were observed with phosphorescence quantum efficiencies(0.183~0.211) in THF solution and triplet lifetime(8.86~13.52 μs) in degassed CH2Cl2 solution.The results show that the attached acyloxy of the long carbon chains at the meso-positions of tetrakis(4-hydroxylphenyl) porphyrin can reduce phosphorescent lifetime and aggregation between molecules.Further,these complexes reveal characteristic of liquid crystal for long carbon chain acyloxy at the meso-positions of porphyrin complexes.It is possible that these new complexes can be used as applicable phosphorescent emitters in organic light emitter devices(OLEDs) and polarized luminescent devices.
2010, 27(6): 691-694
doi: 10.3724/SP.J.1095.2010.90472
Abstract:
A new tetra(p-methoxy-phenyl) porphyrin Sm(Ⅲ) complex was obtained by the reaction of samarium chloride and tetra(p-methoxy-phenyl) porphyrin in THF in a yield of 62.4%.Besides the coordination reaction conditions,ligands and their complexes fluorescence properties were studied.Their structures were identified by UV-Vis,IR,1H NMR and elemental analysis,which show that Sm(Ⅲ) complex has been formed.The reaction conditions were simple and easy to operate.
A new tetra(p-methoxy-phenyl) porphyrin Sm(Ⅲ) complex was obtained by the reaction of samarium chloride and tetra(p-methoxy-phenyl) porphyrin in THF in a yield of 62.4%.Besides the coordination reaction conditions,ligands and their complexes fluorescence properties were studied.Their structures were identified by UV-Vis,IR,1H NMR and elemental analysis,which show that Sm(Ⅲ) complex has been formed.The reaction conditions were simple and easy to operate.
2010, 27(6): 695-699
doi: 10.3724/SP.J.1095.2010.90558
Abstract:
W-MCM-41 mesoporous catalysts were successfully synthesized in an open system with tetraethyl orthosilicate(TEOS) as silica precursor,sodium tungstate as tungsten precursor,and cetyltrimethylammonium bromide(CTAB) as structure-directing reagent.The samples were characterized by means of various techniques and their catalytic properties for the oxidation of cyclohexene were studied.The effects of Si/W molar ratios on the structure and catalytic properties were investigated in details.The results show that the prepared samples retained the ordered mesoporous structure of MCM-41 and exhibited high catalytic properties.The sample synthesized with n(Si)/n(W)=30 exhibited better catalytic property than others.
W-MCM-41 mesoporous catalysts were successfully synthesized in an open system with tetraethyl orthosilicate(TEOS) as silica precursor,sodium tungstate as tungsten precursor,and cetyltrimethylammonium bromide(CTAB) as structure-directing reagent.The samples were characterized by means of various techniques and their catalytic properties for the oxidation of cyclohexene were studied.The effects of Si/W molar ratios on the structure and catalytic properties were investigated in details.The results show that the prepared samples retained the ordered mesoporous structure of MCM-41 and exhibited high catalytic properties.The sample synthesized with n(Si)/n(W)=30 exhibited better catalytic property than others.
2010, 27(6): 700-704
doi: 10.3724/SP.J.1095.2010.90350
Abstract:
Fe3+ doped TiO2/attapulgite composite photocatalyst(Fe3+-TiO2/ATP) was synthesized by acid-catalyzed sol-gel method,and the structure,morphology,light absorption properties and photocatalytic activity under visible light irradiation were investigated.XRD and TEM analyses reveal that the crystalline structure of ATP in the composite photocatalyst was found thermally stable after being treated at 450℃.TiO2 nanoparticles with anatase form were uniformly dispersed on the surface of ATP without aggregation and the average crystallite size of TiO2 nanoparticles in the composite photocatalyst was smaller than that of the neat TiO2.UV-Vis-DRS shows that the doping of Fe3+ could extend the light response of the composite photocatalyst from UV to visible light region.The Fe3+-TiO2/ATP composite photocatalyst exhibited higher photocatalytic activity for the degradation of methyl blue(MB) and the determined apparent reaction rate constant were about 1.37 times that of TiO2/ATP,4.83 times that of P25 and 6.51 times that of neat TiO2,respectively. Furthermore,the composite photocatalyst showed easy separation property compared with neat TiO2 and P25.
Fe3+ doped TiO2/attapulgite composite photocatalyst(Fe3+-TiO2/ATP) was synthesized by acid-catalyzed sol-gel method,and the structure,morphology,light absorption properties and photocatalytic activity under visible light irradiation were investigated.XRD and TEM analyses reveal that the crystalline structure of ATP in the composite photocatalyst was found thermally stable after being treated at 450℃.TiO2 nanoparticles with anatase form were uniformly dispersed on the surface of ATP without aggregation and the average crystallite size of TiO2 nanoparticles in the composite photocatalyst was smaller than that of the neat TiO2.UV-Vis-DRS shows that the doping of Fe3+ could extend the light response of the composite photocatalyst from UV to visible light region.The Fe3+-TiO2/ATP composite photocatalyst exhibited higher photocatalytic activity for the degradation of methyl blue(MB) and the determined apparent reaction rate constant were about 1.37 times that of TiO2/ATP,4.83 times that of P25 and 6.51 times that of neat TiO2,respectively. Furthermore,the composite photocatalyst showed easy separation property compared with neat TiO2 and P25.
2010, 27(6): 705-709
doi: 10.3724/SP.J.1095.2010.90432
Abstract:
ZnS photocatalyst was synthesized in the presence of surfactant cetyltrimethyl ammonium bromide(CTAB).The results of XRD and TEM indicate that the sizes of the ZnS particles obtained are uniform and there is no aggregation phenomenon.The average size of the ZnS particles is about 3.5 nm.The investigation results of the photodegradation efficiency of the different dyes under the UV light irradiation in the presence of photocatalyst ZnS indicate that the photodegradation efficiency of azo dyes with the -N=N- group,such as methyl orange(MO),acid yellow(AY) and acid organgeII(AOII) on the ZnS photocatalyst in 60 min is as high as 88%,illustrating that the dyes with the -N=N- group is easy to be degraded.In addition,the light absorption properties of the dye molecules also play a certain role.Both xylenol organge(XO) and methylene blue(MB) molecules do not contain the -N=N- group.However,the photodegradation efficiencies of XO is as high as about 59.63% due to the largest absorption peak of XO located at 430 nm.Whereas the photodegradation efficiencies of MB is very low due to the largest absorption peak of MB located at 664 nm.
ZnS photocatalyst was synthesized in the presence of surfactant cetyltrimethyl ammonium bromide(CTAB).The results of XRD and TEM indicate that the sizes of the ZnS particles obtained are uniform and there is no aggregation phenomenon.The average size of the ZnS particles is about 3.5 nm.The investigation results of the photodegradation efficiency of the different dyes under the UV light irradiation in the presence of photocatalyst ZnS indicate that the photodegradation efficiency of azo dyes with the -N=N- group,such as methyl orange(MO),acid yellow(AY) and acid organgeII(AOII) on the ZnS photocatalyst in 60 min is as high as 88%,illustrating that the dyes with the -N=N- group is easy to be degraded.In addition,the light absorption properties of the dye molecules also play a certain role.Both xylenol organge(XO) and methylene blue(MB) molecules do not contain the -N=N- group.However,the photodegradation efficiencies of XO is as high as about 59.63% due to the largest absorption peak of XO located at 430 nm.Whereas the photodegradation efficiencies of MB is very low due to the largest absorption peak of MB located at 664 nm.
2010, 27(6): 710-715
doi: 10.3724/SP.J.1095.2010.90480
Abstract:
Activated carbon/CoFe2O4 composite(AC/CoFe2O4,MAC) with magnetic seperation performance was synthesized via a low-temperature refluxing route.Batch experiments were carried out to investigate the adsorption kinetics and equilibrium of methylene blue(MB) onto MAC.The effect of initial pH value on MB adsorbed onto MAC was evaluated.It was found that the adsorption of MB onto MAC was a very rapid process,reaching to the equilibrium within 20 min.The pseudo-second-order rate equation could describe the adsorption kinetics of the MB onto MAC.The equilibrium data could be fitted well with the Langmuir equation.The saturated adsorption capacity obtained from the Langmuir equation was 120.48 mg/g.At lower pH values,adsorption capacity of MAC for MB was small,whereas it increased with increasing pH value.
Activated carbon/CoFe2O4 composite(AC/CoFe2O4,MAC) with magnetic seperation performance was synthesized via a low-temperature refluxing route.Batch experiments were carried out to investigate the adsorption kinetics and equilibrium of methylene blue(MB) onto MAC.The effect of initial pH value on MB adsorbed onto MAC was evaluated.It was found that the adsorption of MB onto MAC was a very rapid process,reaching to the equilibrium within 20 min.The pseudo-second-order rate equation could describe the adsorption kinetics of the MB onto MAC.The equilibrium data could be fitted well with the Langmuir equation.The saturated adsorption capacity obtained from the Langmuir equation was 120.48 mg/g.At lower pH values,adsorption capacity of MAC for MB was small,whereas it increased with increasing pH value.
2010, 27(6): 716-720
doi: 10.3724/SP.J.1095.2010.90501
Abstract:
Inhibitory effects of two Schiff bases N,N'-bis(salicylidene)-1,2-ethylendiamine(SB-Ⅰ) and salcylidene-pyridine-2-yl-amine(SB-Ⅱ) on the corrosion of carbon steel in 1 mol/L HCl solution were studied via mass loss measurement method,polarization and electrochemical impedance spectroscopy.The results show that compounds SB-Ⅰ and SB-Ⅱ have fairly good inhibiting properties for carbon steel corrosion in hydrochloric acid with the best efficiencies of 85% and 92%,respectively,at 20 mmol/L additive concentration,and they belong to anodic inhibitors.
Inhibitory effects of two Schiff bases N,N'-bis(salicylidene)-1,2-ethylendiamine(SB-Ⅰ) and salcylidene-pyridine-2-yl-amine(SB-Ⅱ) on the corrosion of carbon steel in 1 mol/L HCl solution were studied via mass loss measurement method,polarization and electrochemical impedance spectroscopy.The results show that compounds SB-Ⅰ and SB-Ⅱ have fairly good inhibiting properties for carbon steel corrosion in hydrochloric acid with the best efficiencies of 85% and 92%,respectively,at 20 mmol/L additive concentration,and they belong to anodic inhibitors.
2010, 27(6): 721-726
doi: 10.3724/SP.J.1095.2010.90536
Abstract:
The spectroscopic properties of coordination reactions between two Zn prophyrin[5-(p-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin and 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin] and three imidazole(Im) derivatives were studied by means of UV-Vis spectroscopy titrations and fluorescence spectroscopy.The axial coordination reactions were related to different positions of substituent group in Zn prophyrin and the structure of guest.The results show:the axial coordination reaction was carried out in a molar ratio of 1:1,the association constants decreased in the order of K(2-MeIm)>K(N-MeIm)>K(Im),in which the maximum association constant was 5.85×105 L/mol between 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin and 2-MeIm;the association constant would decrease with increasing temperature,which was a disadvantage factor for the reaction;the thermodynamic parameters revealed that the driving force was the change of enthalpy and the reaction was spontaneous;the intensity of fluorescence increased in the system of axial coordination reaction of 5-(p-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin(fluorescence peak:592.9 nm,634.2 nm) with increasing the guest concentration,and the fluorescence quenching exhibited in the system of axial coordination reaction of 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin(fluorescence peak:583.6 nm,629.8 nm). The fluorescence effect was determined by the position of nitryl group in Zn prophyrin and independent of the structure of guest.
The spectroscopic properties of coordination reactions between two Zn prophyrin[5-(p-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin and 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin] and three imidazole(Im) derivatives were studied by means of UV-Vis spectroscopy titrations and fluorescence spectroscopy.The axial coordination reactions were related to different positions of substituent group in Zn prophyrin and the structure of guest.The results show:the axial coordination reaction was carried out in a molar ratio of 1:1,the association constants decreased in the order of K(2-MeIm)>K(N-MeIm)>K(Im),in which the maximum association constant was 5.85×105 L/mol between 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin and 2-MeIm;the association constant would decrease with increasing temperature,which was a disadvantage factor for the reaction;the thermodynamic parameters revealed that the driving force was the change of enthalpy and the reaction was spontaneous;the intensity of fluorescence increased in the system of axial coordination reaction of 5-(p-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin(fluorescence peak:592.9 nm,634.2 nm) with increasing the guest concentration,and the fluorescence quenching exhibited in the system of axial coordination reaction of 5-(o-nitrylphenyl)-10,15,20-triphenyl Zn porphyrin(fluorescence peak:583.6 nm,629.8 nm). The fluorescence effect was determined by the position of nitryl group in Zn prophyrin and independent of the structure of guest.
2010, 27(6): 727-731
doi: 10.3724/SP.J.1095.2010.90562
Abstract:
Zeta potential method was used to select wetting dispersant in preparing 20% diflufenican suspension concentrate,the average particle diameter(Dav) of test system was determined using a laser particle distribution instrument. The results show that all test anionic wetting dispersants, beside sodium lignosulfonate,could make the suspension particle to reach the absolute value of Zeta potential (|ζ|) in excess of 40 mV, and the suspension concentrate was comparatively stable. When mixed anionic wetting dispersants (NNO and Morwet D425) were used instead of single NNO or Morwet D425,|ζ|of the suspension system was higher than that of single system at the same usage amount. When m(NNO):m(Morwet D425)=1:4, and mass fraction of the mixture was 1%,|ζ|could reach the maximum and the average particle diameter of the system was the smallest. The changes of|ζ|and Dav were very small after heat storage treatment, and the corresponding system achieved the best dispersion effect. Thus zeta potential value of the suspension concentrate has a good correlation to the average particle diameter. Therefore the dispersing effect of wetting dispersant in suspension concentrate could be well represented by the zeta potential value.
Zeta potential method was used to select wetting dispersant in preparing 20% diflufenican suspension concentrate,the average particle diameter(Dav) of test system was determined using a laser particle distribution instrument. The results show that all test anionic wetting dispersants, beside sodium lignosulfonate,could make the suspension particle to reach the absolute value of Zeta potential (|ζ|) in excess of 40 mV, and the suspension concentrate was comparatively stable. When mixed anionic wetting dispersants (NNO and Morwet D425) were used instead of single NNO or Morwet D425,|ζ|of the suspension system was higher than that of single system at the same usage amount. When m(NNO):m(Morwet D425)=1:4, and mass fraction of the mixture was 1%,|ζ|could reach the maximum and the average particle diameter of the system was the smallest. The changes of|ζ|and Dav were very small after heat storage treatment, and the corresponding system achieved the best dispersion effect. Thus zeta potential value of the suspension concentrate has a good correlation to the average particle diameter. Therefore the dispersing effect of wetting dispersant in suspension concentrate could be well represented by the zeta potential value.
2010, 27(6): 732-736
doi: 10.3724/SP.J.1095.2010.90588
Abstract:
A new ON-OFF fluorescent chemosensor(triquinolin-8-yl benzene-1,3,5-tricarboxylate,TQBTC) has been synthesized and characterized by FT-IR,elemental analysis and 1H NMR.Fluorescence studies indicate that the acetonitrile-H2O solution of TQBTC shows an emission band centered at 616.0 nm when excited at 253.0 nm.TQBTC could selectively complex with mercury at a coordination ratio of 1:3 result in a linear quenching of the emission.Consequently,TQBTC can be used as a fluorescent chemosensor for selective sensing of Hg(Ⅱ) and a sensitive method of detection of Hg(Ⅱ) has thus been established.The emission of TQBTC is quenched linearly when Hg(Ⅱ) is added quantitatively in the range of 0~30 μmol/L.The detection limit is 0.838 μmol/L.Application of this method to the detection of Hg(Ⅱ) in water samples shows satisfactory results.
A new ON-OFF fluorescent chemosensor(triquinolin-8-yl benzene-1,3,5-tricarboxylate,TQBTC) has been synthesized and characterized by FT-IR,elemental analysis and 1H NMR.Fluorescence studies indicate that the acetonitrile-H2O solution of TQBTC shows an emission band centered at 616.0 nm when excited at 253.0 nm.TQBTC could selectively complex with mercury at a coordination ratio of 1:3 result in a linear quenching of the emission.Consequently,TQBTC can be used as a fluorescent chemosensor for selective sensing of Hg(Ⅱ) and a sensitive method of detection of Hg(Ⅱ) has thus been established.The emission of TQBTC is quenched linearly when Hg(Ⅱ) is added quantitatively in the range of 0~30 μmol/L.The detection limit is 0.838 μmol/L.Application of this method to the detection of Hg(Ⅱ) in water samples shows satisfactory results.
2010, 27(6): 737-741
doi: 10.3724/SP.J.1095.2010.90548
Abstract:
In Tris-HCl buffer solution,a resonance light scattering(RLS) detection method for adenosine disodium triphosphate(ATP) was developed based on RLS signal enhancement due to interactions of ATP with cerium ions in an alkalescent aqueous medium.The enhanced RLS intensity was proportional to ATP content in a range of 2.0~24 μmol/L with a limit of determination(LOD,S/N=3σ) of 51.25 nmol/L.The effects of coexisting substances were investigated.The method has been successfully applied to determining the content of ATP in injection samples with a RSD of 2.29%.
In Tris-HCl buffer solution,a resonance light scattering(RLS) detection method for adenosine disodium triphosphate(ATP) was developed based on RLS signal enhancement due to interactions of ATP with cerium ions in an alkalescent aqueous medium.The enhanced RLS intensity was proportional to ATP content in a range of 2.0~24 μmol/L with a limit of determination(LOD,S/N=3σ) of 51.25 nmol/L.The effects of coexisting substances were investigated.The method has been successfully applied to determining the content of ATP in injection samples with a RSD of 2.29%.
2010, 27(6): 742-744
doi: 10.3724/SP.J.1095.2010.90449
Abstract:
Three kinds of gemini anionic surfactants were synthesized through addition reaction, acylation reaction and hydrolysis from starting materials of octanoyl chloride, decanoyl chloride and lauroyl chloride.The structures of the surfactants were identified by 1H NMR, 13C NMR and IR. The values of critical miscelle concentration(cmc) and surface stress (γcmc) measured at 25℃ decrease with the increase of hydrophobic chain length of the surfactants. The gemini anionic surfactant is able to enhance the collophanite floating capability of oleic acid.
Three kinds of gemini anionic surfactants were synthesized through addition reaction, acylation reaction and hydrolysis from starting materials of octanoyl chloride, decanoyl chloride and lauroyl chloride.The structures of the surfactants were identified by 1H NMR, 13C NMR and IR. The values of critical miscelle concentration(cmc) and surface stress (γcmc) measured at 25℃ decrease with the increase of hydrophobic chain length of the surfactants. The gemini anionic surfactant is able to enhance the collophanite floating capability of oleic acid.
