A series of nanorod-like porous Pd/γ-Al2 O3 catalysts with controllable textural properties and enhanced catalytic performance in 2-ethyl-9,10-anthraquinone(eAQ) hydrogenation for H2 O2 preparation were successfully ...A series of nanorod-like porous Pd/γ-Al2 O3 catalysts with controllable textural properties and enhanced catalytic performance in 2-ethyl-9,10-anthraquinone(eAQ) hydrogenation for H2 O2 preparation were successfully prepared via a facile sol-gel method using aluminum isopropoxide as aluminum precursor and eAQ as structure directing agent,sequential calcination and impregnation process with Na2 PdCl4 solution.The physicochemical properties of the catalysts obtained with different addition amounts of eAQ.were comparatively characterized by XRD,TG-DSC,BET,TEM,CO-TPR,H2-TPR and H2-O2 titration.The results show that addition of eAQ can not only effectively control the textural properties(surface area,pore volume and average pore size) of the catalysts,but also lower their reduction temperature of active metal.Importantly,the catalyst obtained with an addition amount of 4 wt% eAQ shows the highest hydrogenation efficiency of 10.28 g·L^-1,which is 37.3% higher than 7.49 g·L^-1 of the catalyst obtained without eAQ.展开更多
The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H1...The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?展开更多
A long chain aliphatic sulfoxide can be used as an extractant.It can extract almost all metallic ions which can be extracted by tributylphosphate (TBP).The extraction of gold was studied by Chekushin,V. S. and Mojski,...A long chain aliphatic sulfoxide can be used as an extractant.It can extract almost all metallic ions which can be extracted by tributylphosphate (TBP).The extraction of gold was studied by Chekushin,V. S. and Mojski,M.using petroleum sulfoxide and n-dioctyl sulfoxide(DOSO) as an extractant respectively.展开更多
By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with e...By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.展开更多
This study aimed to investigate the ability of the novel materials D-α-tocopheryl poly(2-ethyl-2-oxazoline) succinate(TPOS) to construct pH-sensitive liposomes. TPOS was initially synthesized and characterized by TLC...This study aimed to investigate the ability of the novel materials D-α-tocopheryl poly(2-ethyl-2-oxazoline) succinate(TPOS) to construct pH-sensitive liposomes. TPOS was initially synthesized and characterized by TLC, FTIR, and ~1H-NMR. The buffering capacity of polyethylene glycol-distearoyl phosphatidylethanolamine(PEG-DSPE) and TPOS was determined by acid-base titration, and TPOS displayed a slower downtrend and gentler slope of titration curve than PEG-DSPE within pH 7.4–5.0. Studies on the in vitro drug release demonstrated that TPOS modified docetaxel(DOC) liposomes(TPOS-DOC-L) had a slower drugrelease rate at pH 7.4 similar to PEGylated-DOC liposomes(PEG-DOC-L), whereas the release rate reached approximately 86.92% ± 1.69% at pH 6.4. In vitro cellular uptake assays by microplate reader, and flow cytometry revealed that TPOS modified coumarin 6 liposomes(TPOS-C6-L) had stronger cellular uptake at pH 6.4 than that at pH 7.4( P < 0.01). Conversely, for PEGylated C6 liposomes(PEG-C6-L) and conventional C6 liposomes(C6-L), very similar cellular uptakes were exhibited at different pH values. Confocal laser scanning microscopy images showed that PEG-C6-L and C6-L were mainly located in lysosomes. By contrast, TPOS-C6-L showed broader cytoplasmic release and distribution at 4 h. MTT assay showed that the cytotoxicity of TPOS-DOC-L was similar to that of PEG-DOC-L and conventional DOC liposomes(DOC-L) at the same DOC concentration and at pH 7.4, but was much lower than those at pH 6.4 after 48 h of incubation. The apoptosis of PEG-DOC-L and DOC-L had no remarkable improvement with decreased pH from 7.4 to 6.4. Meanwhile, TPOS-DOC-Lsignificantly induced the apoptosis of HeLa cells with decreased pH. Therefore, TPOS can be a biomaterial for the construction of a pH-sensitive drug delivery system.展开更多
A practical synthesis of （S）-N-（2-ethyl-6-methylphenyl）alanine, a key intermediate for （S）-metolachlor, was completed by means of lipase-catalyzed hydrolytic kinetic resolution and chemical racemization of the r...A practical synthesis of （S）-N-（2-ethyl-6-methylphenyl）alanine, a key intermediate for （S）-metolachlor, was completed by means of lipase-catalyzed hydrolytic kinetic resolution and chemical racemization of the remaining ester. The effects of operating temperature and enzyme concentration on the activity and enantioselectivity of enzyme were initially studied, and it was found that the enantioselectivity of CAL-B towards the resolution was not high enough to obtain enantiomerically pure compound（E=12.1）. When diethyl ether（15%, volume fraction） was added in the reaction medium, the lipase gave an excellent enantioselectivity（E=117.8）, which is about 9.7-fold that in pure buffered aqueous solution. For overcoming the limitation of a maximum theoretical yield of 50%, the acid product was separated from the remaining ester by a simple extraction procedure and the remaining ester was racemized with aldehyde and acetic acid under microwave irradiation or conventional heating condition, The results show the microwave irradiation was more effective than the conventional heating method and gave the desired （R,S）-N-（2- ethyl-6-methylphenyl）alanine methyl ester a high yield（92%） with R/S=50/50 in 1 h.展开更多
The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the co...The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.展开更多
The complex [Fe(C14H14NO2)3]2H2O has been prepared by reaction of N-p-methylphenyl-3-hydroxy-2-ethyl-4-pyridinone with FeCl36H2O. A single-crystal X-ray study shows that the iron atoms lie in a trigonally distorted oc...The complex [Fe(C14H14NO2)3]2H2O has been prepared by reaction of N-p-methylphenyl-3-hydroxy-2-ethyl-4-pyridinone with FeCl36H2O. A single-crystal X-ray study shows that the iron atoms lie in a trigonally distorted octahedral environment coordinated to the hydroxy and ketone oxygen atoms of three ligands in the mer configuration Mr=773.57(C42H46N3O8Fe). The crystal is hexagonal with space group P31c; a=15.943(2), c=17.612(4)? V=3877.0(12)?, Z=4, Dc=1.325g/cm3, m=0.445mm-1, F(000)=1634, R=0.0446, wR= 0.1154 for 3085 reflections with I >2s(I). The bond lengths from iron to oxygens are 1.980(1)?for the ketone oxygens and 2.071(1)?for the hydroxy oxygens. The molecule exhibits the expected propeller shape, and the angle of the trigonal twist is 48.37. The dihedral angles are 0.5(2)?between chelate ring plane and pyridine ring plane and 71.31(7)?between pyridine ring plane and benzene ring plane. The solvent H2O(O(3) and O(4)) molecules are linked with O(2) and O(1) by hydrogen bonds with bond lengths 2.900(1) and 2.999(1)? respectively.展开更多
Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as...Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as food and liquids that can be routed for human exposure. One of the most used phthalates is Diethylhexyl phthalate (DEHP). Diethylhexyl phthalate and its metabolite 2-ethyl-1-hexanol (2-EH) have demonstrated biological effects which merit further evaluation. In this work, we expand on our previous work with DEHP and screen the 2-EH metabolite for different cell death endpoints such as growth inhibition, apoptosis, autophagy, caspase activation, DNA fragmentation, and cell cycle arrest using fluorophores and the NC3000 instrument. Significant results (p 0.05) revealed higher toxicity for the 2-EH metabolite when compared to DEHP. Also, 2-EH presented apoptosis induction with characteristic hallmarks, such as loss of mitochondrial membrane potential, caspase activation, DNA fragmentation and cell cycle arrest at the S phase. In addition, the presence of autophagosome was detected through L3CB protein staining. We conclude that 2-EH presents differences in cell death endpoints that interestingly differ from the DEHP parent compound. Further studies are needed to establish the molecular pathways responsible for the observed effects.展开更多
A new phloretin derivative 1 3-[2-(4-hydroxy-phenyl)-ethyl]-benzo[d] isoxazole-4,6-diol (yield 63%) was synthesized from phloretin by carbonyl nucleophilic addition condensation reaction. Its structure was characteriz...A new phloretin derivative 1 3-[2-(4-hydroxy-phenyl)-ethyl]-benzo[d] isoxazole-4,6-diol (yield 63%) was synthesized from phloretin by carbonyl nucleophilic addition condensation reaction. Its structure was characterized by 1H NMR, 13C NMR and HR-MS. The phloretin, compound 1, resveratrol and acetylated resveratrol were determined by comparing them with paclitaxel. Anti-tumor activity of alcohol on SPC-A1, EC109, A549, MCF-7 and MDA-MB-231 cell lines. Compound 1 showed better antitumor activity than docetaxel against A549 tumor cells.展开更多
基金Supported by the 2016 Wuhan Yellow Crane Talents(Science)ProgramOne Hundred Talents Project of Guangzhou University(No.69-18ZX10016)
文摘A series of nanorod-like porous Pd/γ-Al2 O3 catalysts with controllable textural properties and enhanced catalytic performance in 2-ethyl-9,10-anthraquinone(eAQ) hydrogenation for H2 O2 preparation were successfully prepared via a facile sol-gel method using aluminum isopropoxide as aluminum precursor and eAQ as structure directing agent,sequential calcination and impregnation process with Na2 PdCl4 solution.The physicochemical properties of the catalysts obtained with different addition amounts of eAQ.were comparatively characterized by XRD,TG-DSC,BET,TEM,CO-TPR,H2-TPR and H2-O2 titration.The results show that addition of eAQ can not only effectively control the textural properties(surface area,pore volume and average pore size) of the catalysts,but also lower their reduction temperature of active metal.Importantly,the catalyst obtained with an addition amount of 4 wt% eAQ shows the highest hydrogenation efficiency of 10.28 g·L^-1,which is 37.3% higher than 7.49 g·L^-1 of the catalyst obtained without eAQ.
基金This work was supported by the foundation of Natural Science Research of Jiangsu Education Department (02KJB150007)
文摘The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?
基金Projects supported by the Fund of National Natural Science Foundation
文摘A long chain aliphatic sulfoxide can be used as an extractant.It can extract almost all metallic ions which can be extracted by tributylphosphate (TBP).The extraction of gold was studied by Chekushin,V. S. and Mojski,M.using petroleum sulfoxide and n-dioctyl sulfoxide(DOSO) as an extractant respectively.
基金Supported by the National Natural Science Foundation of China(Grant no.59503002)and Polymer Physics Laboratory of Changchun Institute of Applied Chemistry,Chinese Academy of Sciences
文摘By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.
基金supported by National Natural Science Foundation of China (81102394)Natural Science Foundation of Liaoning Province (20170540575)
文摘This study aimed to investigate the ability of the novel materials D-α-tocopheryl poly(2-ethyl-2-oxazoline) succinate(TPOS) to construct pH-sensitive liposomes. TPOS was initially synthesized and characterized by TLC, FTIR, and ~1H-NMR. The buffering capacity of polyethylene glycol-distearoyl phosphatidylethanolamine(PEG-DSPE) and TPOS was determined by acid-base titration, and TPOS displayed a slower downtrend and gentler slope of titration curve than PEG-DSPE within pH 7.4–5.0. Studies on the in vitro drug release demonstrated that TPOS modified docetaxel(DOC) liposomes(TPOS-DOC-L) had a slower drugrelease rate at pH 7.4 similar to PEGylated-DOC liposomes(PEG-DOC-L), whereas the release rate reached approximately 86.92% ± 1.69% at pH 6.4. In vitro cellular uptake assays by microplate reader, and flow cytometry revealed that TPOS modified coumarin 6 liposomes(TPOS-C6-L) had stronger cellular uptake at pH 6.4 than that at pH 7.4( P < 0.01). Conversely, for PEGylated C6 liposomes(PEG-C6-L) and conventional C6 liposomes(C6-L), very similar cellular uptakes were exhibited at different pH values. Confocal laser scanning microscopy images showed that PEG-C6-L and C6-L were mainly located in lysosomes. By contrast, TPOS-C6-L showed broader cytoplasmic release and distribution at 4 h. MTT assay showed that the cytotoxicity of TPOS-DOC-L was similar to that of PEG-DOC-L and conventional DOC liposomes(DOC-L) at the same DOC concentration and at pH 7.4, but was much lower than those at pH 6.4 after 48 h of incubation. The apoptosis of PEG-DOC-L and DOC-L had no remarkable improvement with decreased pH from 7.4 to 6.4. Meanwhile, TPOS-DOC-Lsignificantly induced the apoptosis of HeLa cells with decreased pH. Therefore, TPOS can be a biomaterial for the construction of a pH-sensitive drug delivery system.
基金Supported by the National Natural Science Foundation of China(No.20802025)the Hi-Tech Research and Development Program of China(No.2007AA021306)Jilin Provincial Science & Technology Sustentation Program,China(No.20070553)
文摘A practical synthesis of （S）-N-（2-ethyl-6-methylphenyl）alanine, a key intermediate for （S）-metolachlor, was completed by means of lipase-catalyzed hydrolytic kinetic resolution and chemical racemization of the remaining ester. The effects of operating temperature and enzyme concentration on the activity and enantioselectivity of enzyme were initially studied, and it was found that the enantioselectivity of CAL-B towards the resolution was not high enough to obtain enantiomerically pure compound（E=12.1）. When diethyl ether（15%, volume fraction） was added in the reaction medium, the lipase gave an excellent enantioselectivity（E=117.8）, which is about 9.7-fold that in pure buffered aqueous solution. For overcoming the limitation of a maximum theoretical yield of 50%, the acid product was separated from the remaining ester by a simple extraction procedure and the remaining ester was racemized with aldehyde and acetic acid under microwave irradiation or conventional heating condition, The results show the microwave irradiation was more effective than the conventional heating method and gave the desired （R,S）-N-（2- ethyl-6-methylphenyl）alanine methyl ester a high yield（92%） with R/S=50/50 in 1 h.
基金the Natural Science Foundation of Jiangsu Education Department (No. 02KJB15007)
文摘The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.
基金the Foundation of Returning Personal from Overseas Study of Jiangsu Education Department.
文摘The complex [Fe(C14H14NO2)3]2H2O has been prepared by reaction of N-p-methylphenyl-3-hydroxy-2-ethyl-4-pyridinone with FeCl36H2O. A single-crystal X-ray study shows that the iron atoms lie in a trigonally distorted octahedral environment coordinated to the hydroxy and ketone oxygen atoms of three ligands in the mer configuration Mr=773.57(C42H46N3O8Fe). The crystal is hexagonal with space group P31c; a=15.943(2), c=17.612(4)? V=3877.0(12)?, Z=4, Dc=1.325g/cm3, m=0.445mm-1, F(000)=1634, R=0.0446, wR= 0.1154 for 3085 reflections with I >2s(I). The bond lengths from iron to oxygens are 1.980(1)?for the ketone oxygens and 2.071(1)?for the hydroxy oxygens. The molecule exhibits the expected propeller shape, and the angle of the trigonal twist is 48.37. The dihedral angles are 0.5(2)?between chelate ring plane and pyridine ring plane and 71.31(7)?between pyridine ring plane and benzene ring plane. The solvent H2O(O(3) and O(4)) molecules are linked with O(2) and O(1) by hydrogen bonds with bond lengths 2.900(1) and 2.999(1)? respectively.
文摘Phthalates have been used in a wide variety of consumer goods. Their versatility as plasticizers has translated into worldwide use in a vast array of consumer products. These compounds can leach into matrices, such as food and liquids that can be routed for human exposure. One of the most used phthalates is Diethylhexyl phthalate (DEHP). Diethylhexyl phthalate and its metabolite 2-ethyl-1-hexanol (2-EH) have demonstrated biological effects which merit further evaluation. In this work, we expand on our previous work with DEHP and screen the 2-EH metabolite for different cell death endpoints such as growth inhibition, apoptosis, autophagy, caspase activation, DNA fragmentation, and cell cycle arrest using fluorophores and the NC3000 instrument. Significant results (p 0.05) revealed higher toxicity for the 2-EH metabolite when compared to DEHP. Also, 2-EH presented apoptosis induction with characteristic hallmarks, such as loss of mitochondrial membrane potential, caspase activation, DNA fragmentation and cell cycle arrest at the S phase. In addition, the presence of autophagosome was detected through L3CB protein staining. We conclude that 2-EH presents differences in cell death endpoints that interestingly differ from the DEHP parent compound. Further studies are needed to establish the molecular pathways responsible for the observed effects.
文摘A new phloretin derivative 1 3-[2-(4-hydroxy-phenyl)-ethyl]-benzo[d] isoxazole-4,6-diol (yield 63%) was synthesized from phloretin by carbonyl nucleophilic addition condensation reaction. Its structure was characterized by 1H NMR, 13C NMR and HR-MS. The phloretin, compound 1, resveratrol and acetylated resveratrol were determined by comparing them with paclitaxel. Anti-tumor activity of alcohol on SPC-A1, EC109, A549, MCF-7 and MDA-MB-231 cell lines. Compound 1 showed better antitumor activity than docetaxel against A549 tumor cells.
