Two novel reactive monomers 2,4 bis(2 allyl phenoxy) 6 N,N dialkylamino 1,3,5 triazine (alkyl=methyl, ethyl) were synthesized in one pot reaction of cyanuric chloride, 2 allyl phenol with dialkylamine in acetone/water...Two novel reactive monomers 2,4 bis(2 allyl phenoxy) 6 N,N dialkylamino 1,3,5 triazine (alkyl=methyl, ethyl) were synthesized in one pot reaction of cyanuric chloride, 2 allyl phenol with dialkylamine in acetone/water in the presence of aq. NaOH. The products have been characterized by FTIR, 1H NMR, 13 C NMR and elemental analysis.展开更多
Solanesyl bromide(Ⅱ) was reacted with diethanolamine to give solanesyl diethanolamine(Ⅲ) which was acylated with 3,4,5 trimethoxybenzoyl chloride, acetic anhydride, benzoyl chloride and cinnamyl chloride to give N,N...Solanesyl bromide(Ⅱ) was reacted with diethanolamine to give solanesyl diethanolamine(Ⅲ) which was acylated with 3,4,5 trimethoxybenzoyl chloride, acetic anhydride, benzoyl chloride and cinnamyl chloride to give N,N di[(3,4,5 trimethoxybenzoyloxy)ethyl]solanesylamine(Ⅳ), N,N di[(acetyloxy)ethyl] solanesylamine(Ⅴ), N,N di[(benzoyloxy)ethyl]solanesylamine(Ⅵ), N,N di[(cinnyloxy)ethyl]solanesylamine(Ⅶ) respectively. The structures of compounds Ⅲ～Ⅶ were confirmed by IR, 1H NMR, MS and elemental analysis.展开更多
Terephthalic acid(PTA) is practically one of the main materials of polyester. Its corresponding solid-liquid equilibrium data will provide essential support for industry design and further theoretical studies. In this...Terephthalic acid(PTA) is practically one of the main materials of polyester. Its corresponding solid-liquid equilibrium data will provide essential support for industry design and further theoretical studies. In this work,solid-liquid equilibriums of terephthalic acid in four solvents, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulphoxide and N-methyl-2-ketopyrrolidene, were determined in the temperature range from 293.15 K to 364.6 K by dynamic method. All these data were regressed by λh model, Wilson model and NRTL model, average absolute relative deviations of which are 1.25%, 15.02% and 7.22% respectively. It indicates that λh model is mostsuitable for description of the solid-liquid equilibrium containing PTA.展开更多
Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with...Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with an ionic liquid(IL)linkage via the one‐pot reaction of imidazole‐TsDPEN‐N‐Boc with 3‐(trimethoxysilyl)propyl bromide in the SBA‐15 mesopores.After coordination to Rh,the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation,achieving 97%conversion with 93%ee,which was comparable to their homogeneous counterparts.The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage(93 h^(–1)vs.33 h^(–1)),attributed to the phase transfer and formate‐enriching ability of the IL linkage.Furthermore,the effect of the pH on the reaction rate of the solid catalyst was investigated,preventing reaction rate retardation during the catalytic process.The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.展开更多
The reaction of di(2-pyridyl)ketone with ethylenediamine produced hexadentate Schiff base 1 which can be reduced to form a new ligand N,N-bis(di(2-pyridyl)-methyl)ethylene- diamine (BDPM) in ethanol solution. The two ...The reaction of di(2-pyridyl)ketone with ethylenediamine produced hexadentate Schiff base 1 which can be reduced to form a new ligand N,N-bis(di(2-pyridyl)-methyl)ethylene- diamine (BDPM) in ethanol solution. The two compounds were characterized by elemental analyses and spectroscopic methods. Their structures were determined by X-ray diffraction study. Crystal data for 1: C24H20N6, Mr = 392.5, monoclinic, P21/c, a = 13.871(3), b = 13.510(2), c = 12.153(2) ? b = 112.97(2)? Z = 4, V = 2094.1(6) ?, Dc = 1.245 g/cm3, m(MoKa) = 0.078 mm-1, F(000) = 824, the final R = 0.0545 and wR = 0.0557 for 2048 observed reflections (I > 2s(I)); for BDPM: C24H24N6, Mr = 396.49, monoclinic, C2/c, a = 21.411(3), b = 8.053(1), c = 11.868(1) ? b = 92.63(1)? Z = 4, V = 2044.2(4) 3, Dc = 1.288 g/cm3, m(MoKa) = 0.080 mm-1, F(000) = 840, the final R = 0.0401 and wR = 0.0939 for 1673 observed reflections (I > 2s(I)).展开更多
The title complex was obtained by reaction of hydrated neodymium(Ⅲ) nitrate with N,N-disalicyclideneethylenediamine in DMSO. The complex [Nd(C_6H_4OHCHNC_2H_4NCHC_6H_4OH)(NO_3)_3(CH_3SOCH_3)] crystallizes in monoclin...The title complex was obtained by reaction of hydrated neodymium(Ⅲ) nitrate with N,N-disalicyclideneethylenediamine in DMSO. The complex [Nd(C_6H_4OHCHNC_2H_4NCHC_6H_4OH)(NO_3)_3(CH_3SOCH_3)] crystallizes in monoclinic system, space group- P2_1/n, a=9.663(2), b=16.610(6),c=16.322(5),β=102.77(2)°,V=2555(3),M_r=676.71,Z=4,Dx=1.759 gcm-3. The coordination number of Nd(Ⅲ) is 9 with the geometry of a monocapped square antiprism.All of coordination atoms are oxygen atoms from three bidentate nitrate groups, two dischiff base molecules and one DMSO molecule.展开更多
The extraction of cadmium and zinc with di-(2-ethylhexyl)-dithiophosphoric acid(D2EHDTPA)-toluene and D2EHDTPA-trioctyl amine(TOA)-toluene has been investigated. Infrared spectrum analysis, the nuclear magnetic resona...The extraction of cadmium and zinc with di-(2-ethylhexyl)-dithiophosphoric acid(D2EHDTPA)-toluene and D2EHDTPA-trioctyl amine(TOA)-toluene has been investigated. Infrared spectrum analysis, the nuclear magnetic resonance spectrum(NMR) analysis and conductivity measurements confirm that the probable structures of the extracted complexes are CdA2 and ZnA2. Cadmium can be extracted by D2EHDTPA very easily. Almost all the cadmium can be extracted, but stripping of cadmium from the organic phase is very difficult. When a mixture of D2EHDTPA and TOA is used, selective extraction of cadmium from zinc sulfate solution can be achieved. Cadmium can be easily stripped from the organic phase.展开更多
Four geometric mer-isomers in the [Co(2,3-tri)(cmen)Cl]2+ system have been synthesized and well separated (2,3-tri = N-(3-aminoethyl)-1,3-propanediamine; cmen = 1,2-di- aminopropane). Their structures in DMSO-d6 solut...Four geometric mer-isomers in the [Co(2,3-tri)(cmen)Cl]2+ system have been synthesized and well separated (2,3-tri = N-(3-aminoethyl)-1,3-propanediamine; cmen = 1,2-di- aminopropane). Their structures in DMSO-d6 solution have been uniquely assigned by using 2D- NMR techniques (gCOSY and NOESY).展开更多
A microporous luminescent metal-organic framework [Zn4L2（H2O）2]＇（H2O）m（DMA）n （1） （H4L=5,5＇-（（1H-pyrazole-3,5-di- carbonyl）bis（azanediyl））diisophthalic acid, DMA=N,N-dimethylacetamide） was synthesized...A microporous luminescent metal-organic framework [Zn4L2（H2O）2]＇（H2O）m（DMA）n （1） （H4L=5,5＇-（（1H-pyrazole-3,5-di- carbonyl）bis（azanediyl））diisophthalic acid, DMA=N,N-dimethylacetamide） was synthesized and characterized by infrared ra- diation （IR）, thermogravimetric analyses （TGA）, powder X-ray diffraction spectra （PXRD） and X-ray diffraction. Complex 1 has a three dimensional （3D） framework, which can be simplified as 5,5,5,5-c net with the Schlafi symbol of {43.64.83} {44.65.8 } {45.65 }2. This luminescent metal-organic framework （MOF） shows selectively sensitive to nitrobenzene and series of nitroaromatic explosives such as 4-nitrotoluene, 1,4-dinitrobenzene, 1,3-dinitrobenzene and 2,4-dinitrotoluene, and exhibits well recyclability. So complex 1 could be used to detect nitroaromatic explosives as a selective sensing material.展开更多
Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA...Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA1580-PEG4600-PAA1580),we designed and synthesized poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA-PEG-PAA)with shorter length of PAA chain by decreasing reaction temperature for preparing PAA-PEG-PAA hydrogel solution containing doxorubicin(DOX).The PAA-PEG-PAA was synthesized via the Michael-addition polymerization.The characteristic of PAA-PEG-PAA was evaluated.The PAA-PEG-PAA hydrogel solution was prepared and investigated.DOX-loaded PAA-PEG-PAA hydrogel solution was prepared,and its in vitro DOX release and in vitro anti-tumor activity were evaluated.Our results indicated that the viscosity of PAA-PEG-PAA hydrogel solution was concentration-and temperature-dependent.The sol-gel transition temperature of PAA-PEG-PAA hydrogel solution(12%,w/w)ranged from 35 to 29℃,and its pH ranged from 6.0 to 7.4.The released DOX from DOX-loaded PAA-PEG-PAA hydrogel showed sustained release characteristics.The in vitro anti-tumor activity of DOX-loaded PAA-PEG-PAA hydrogel was confirmed in B16 F10 cell line.Considering the acidic tumor microenvironment,this DOX-loaded PAA-PEG-PAA hydrogel solution would be easy in situ administration for intra-tumor injection or para-tumor injection forming hydrogel at body temperature.We suggested that this DOX-loaded PAA-PEG-PAAhydrogel solution,if containing photothermal conversion agents,would have a potential further use for photothermal therapy.展开更多
文摘Two novel reactive monomers 2,4 bis(2 allyl phenoxy) 6 N,N dialkylamino 1,3,5 triazine (alkyl=methyl, ethyl) were synthesized in one pot reaction of cyanuric chloride, 2 allyl phenol with dialkylamine in acetone/water in the presence of aq. NaOH. The products have been characterized by FTIR, 1H NMR, 13 C NMR and elemental analysis.
文摘Solanesyl bromide(Ⅱ) was reacted with diethanolamine to give solanesyl diethanolamine(Ⅲ) which was acylated with 3,4,5 trimethoxybenzoyl chloride, acetic anhydride, benzoyl chloride and cinnamyl chloride to give N,N di[(3,4,5 trimethoxybenzoyloxy)ethyl]solanesylamine(Ⅳ), N,N di[(acetyloxy)ethyl] solanesylamine(Ⅴ), N,N di[(benzoyloxy)ethyl]solanesylamine(Ⅵ), N,N di[(cinnyloxy)ethyl]solanesylamine(Ⅶ) respectively. The structures of compounds Ⅲ～Ⅶ were confirmed by IR, 1H NMR, MS and elemental analysis.
基金Supported by China Petroleum & Chemical Corporation(No.200049).
文摘Terephthalic acid(PTA) is practically one of the main materials of polyester. Its corresponding solid-liquid equilibrium data will provide essential support for industry design and further theoretical studies. In this work,solid-liquid equilibriums of terephthalic acid in four solvents, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulphoxide and N-methyl-2-ketopyrrolidene, were determined in the temperature range from 293.15 K to 364.6 K by dynamic method. All these data were regressed by λh model, Wilson model and NRTL model, average absolute relative deviations of which are 1.25%, 15.02% and 7.22% respectively. It indicates that λh model is mostsuitable for description of the solid-liquid equilibrium containing PTA.
文摘Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with an ionic liquid(IL)linkage via the one‐pot reaction of imidazole‐TsDPEN‐N‐Boc with 3‐(trimethoxysilyl)propyl bromide in the SBA‐15 mesopores.After coordination to Rh,the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation,achieving 97%conversion with 93%ee,which was comparable to their homogeneous counterparts.The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage(93 h^(–1)vs.33 h^(–1)),attributed to the phase transfer and formate‐enriching ability of the IL linkage.Furthermore,the effect of the pH on the reaction rate of the solid catalyst was investigated,preventing reaction rate retardation during the catalytic process.The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.
基金This work was financially supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars State Educational Ministry
文摘The reaction of di(2-pyridyl)ketone with ethylenediamine produced hexadentate Schiff base 1 which can be reduced to form a new ligand N,N-bis(di(2-pyridyl)-methyl)ethylene- diamine (BDPM) in ethanol solution. The two compounds were characterized by elemental analyses and spectroscopic methods. Their structures were determined by X-ray diffraction study. Crystal data for 1: C24H20N6, Mr = 392.5, monoclinic, P21/c, a = 13.871(3), b = 13.510(2), c = 12.153(2) ? b = 112.97(2)? Z = 4, V = 2094.1(6) ?, Dc = 1.245 g/cm3, m(MoKa) = 0.078 mm-1, F(000) = 824, the final R = 0.0545 and wR = 0.0557 for 2048 observed reflections (I > 2s(I)); for BDPM: C24H24N6, Mr = 396.49, monoclinic, C2/c, a = 21.411(3), b = 8.053(1), c = 11.868(1) ? b = 92.63(1)? Z = 4, V = 2044.2(4) 3, Dc = 1.288 g/cm3, m(MoKa) = 0.080 mm-1, F(000) = 840, the final R = 0.0401 and wR = 0.0939 for 1673 observed reflections (I > 2s(I)).
文摘The title complex was obtained by reaction of hydrated neodymium(Ⅲ) nitrate with N,N-disalicyclideneethylenediamine in DMSO. The complex [Nd(C_6H_4OHCHNC_2H_4NCHC_6H_4OH)(NO_3)_3(CH_3SOCH_3)] crystallizes in monoclinic system, space group- P2_1/n, a=9.663(2), b=16.610(6),c=16.322(5),β=102.77(2)°,V=2555(3),M_r=676.71,Z=4,Dx=1.759 gcm-3. The coordination number of Nd(Ⅲ) is 9 with the geometry of a monocapped square antiprism.All of coordination atoms are oxygen atoms from three bidentate nitrate groups, two dischiff base molecules and one DMSO molecule.
基金Supported by the National Natural Science Foundation of China(No.59474009).
文摘The extraction of cadmium and zinc with di-(2-ethylhexyl)-dithiophosphoric acid(D2EHDTPA)-toluene and D2EHDTPA-trioctyl amine(TOA)-toluene has been investigated. Infrared spectrum analysis, the nuclear magnetic resonance spectrum(NMR) analysis and conductivity measurements confirm that the probable structures of the extracted complexes are CdA2 and ZnA2. Cadmium can be extracted by D2EHDTPA very easily. Almost all the cadmium can be extracted, but stripping of cadmium from the organic phase is very difficult. When a mixture of D2EHDTPA and TOA is used, selective extraction of cadmium from zinc sulfate solution can be achieved. Cadmium can be easily stripped from the organic phase.
文摘Four geometric mer-isomers in the [Co(2,3-tri)(cmen)Cl]2+ system have been synthesized and well separated (2,3-tri = N-(3-aminoethyl)-1,3-propanediamine; cmen = 1,2-di- aminopropane). Their structures in DMSO-d6 solution have been uniquely assigned by using 2D- NMR techniques (gCOSY and NOESY).
基金supported by the National Basic Research Program of China (2014CB845600)the National Natural Science of Foundation of China (21371102, 21421001)+1 种基金the MOE Innovation Team of China (IRT13022)the China Postdoctoral Science Foundation funded project (2015M571260)
文摘A microporous luminescent metal-organic framework [Zn4L2（H2O）2]＇（H2O）m（DMA）n （1） （H4L=5,5＇-（（1H-pyrazole-3,5-di- carbonyl）bis（azanediyl））diisophthalic acid, DMA=N,N-dimethylacetamide） was synthesized and characterized by infrared ra- diation （IR）, thermogravimetric analyses （TGA）, powder X-ray diffraction spectra （PXRD） and X-ray diffraction. Complex 1 has a three dimensional （3D） framework, which can be simplified as 5,5,5,5-c net with the Schlafi symbol of {43.64.83} {44.65.8 } {45.65 }2. This luminescent metal-organic framework （MOF） shows selectively sensitive to nitrobenzene and series of nitroaromatic explosives such as 4-nitrotoluene, 1,4-dinitrobenzene, 1,3-dinitrobenzene and 2,4-dinitrotoluene, and exhibits well recyclability. So complex 1 could be used to detect nitroaromatic explosives as a selective sensing material.
基金The National Key Research and Development Program of China(Grant No.2017YFA0205600)the National Natural Science Foundation of China(Grant No.81773646)the Innovation Team of the Ministry of Education(Grant No.BMU2017TD003)
文摘Many pH-and temperature-responsive polymers have been designed for preparing hydrogel.In the present study,in order to decrease the pH sensitivity of reported poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA1580-PEG4600-PAA1580),we designed and synthesized poly(amidoamine)-poly(ethyleneglycol)-poly(amidoamine)(PAA-PEG-PAA)with shorter length of PAA chain by decreasing reaction temperature for preparing PAA-PEG-PAA hydrogel solution containing doxorubicin(DOX).The PAA-PEG-PAA was synthesized via the Michael-addition polymerization.The characteristic of PAA-PEG-PAA was evaluated.The PAA-PEG-PAA hydrogel solution was prepared and investigated.DOX-loaded PAA-PEG-PAA hydrogel solution was prepared,and its in vitro DOX release and in vitro anti-tumor activity were evaluated.Our results indicated that the viscosity of PAA-PEG-PAA hydrogel solution was concentration-and temperature-dependent.The sol-gel transition temperature of PAA-PEG-PAA hydrogel solution(12%,w/w)ranged from 35 to 29℃,and its pH ranged from 6.0 to 7.4.The released DOX from DOX-loaded PAA-PEG-PAA hydrogel showed sustained release characteristics.The in vitro anti-tumor activity of DOX-loaded PAA-PEG-PAA hydrogel was confirmed in B16 F10 cell line.Considering the acidic tumor microenvironment,this DOX-loaded PAA-PEG-PAA hydrogel solution would be easy in situ administration for intra-tumor injection or para-tumor injection forming hydrogel at body temperature.We suggested that this DOX-loaded PAA-PEG-PAAhydrogel solution,if containing photothermal conversion agents,would have a potential further use for photothermal therapy.
