5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated...5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.展开更多
2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the t...2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324(2),b = 0.6454(3),c = 0.7062(3) nm,α= 111.550(4),β= 95.505(4),γ= 113.395(4)°,V = 0.23595(16) nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F(000) = 126,R = 0.0304 and wR = 0.0907.展开更多
AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resi...AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.展开更多
An efficient synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions...An efficient synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.展开更多
The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex...The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938(3),b = 1.9422(5),c = 0.9406(2) nm,β = 121.891(4)°,V = 2.0066(9) nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ(MoKα) = 4.209 mm?1,F(000) = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ(I).In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.展开更多
The title compound N,N'-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylene diamine (DPTDEDA, C12H26N2O4P2S2) was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylene...The title compound N,N'-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylene diamine (DPTDEDA, C12H26N2O4P2S2) was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557(16), b = 11.299(12), c = 12.163(13)A,β = 98.707(19)^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ(MoKa) = 0.447 mm^-1, Mr = 388.41, V = 1977(4)A3, F(000) = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections (I 〉 2σ(I)). X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.展开更多
The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as ...The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17~25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ 〉2σ(Ⅰ) were used in the structure solution and refinement.展开更多
The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catal...The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.展开更多
Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxa...Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)(H2O)4]·3H2O}n (M = Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.展开更多
3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)pyrrol-2-yl)pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·(CH3OH)2, belongs to the orthorhombic system, space group ...3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)pyrrol-2-yl)pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·(CH3OH)2, belongs to the orthorhombic system, space group Pccn with a = 18.094(2), b = 11.6890(16), c = 13.3629(19) , V = 2826.3(7) 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F(000) = 1080 and μ(MoKα) = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ(I), and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.展开更多
A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of iodine and 1,4- bis(triphenylphosphonium)-2-butene peroxodisulfate.
Two novel zinc(Ⅱ) coordination polymers, [Zn2(BCB)(CH3OH)(μ3-OH)]n(1) and {[Zn2(BCB)(μ3-OH)(H2O)2]·CH3OH}n (2), have been constructed from 3,5-bis(2-carboxylphenoxy)benzoic acid(H3BCB) an...Two novel zinc(Ⅱ) coordination polymers, [Zn2(BCB)(CH3OH)(μ3-OH)]n(1) and {[Zn2(BCB)(μ3-OH)(H2O)2]·CH3OH}n (2), have been constructed from 3,5-bis(2-carboxylphenoxy)benzoic acid(H3BCB) and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn4(COO)4(μ3-OH)2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.展开更多
The reactions of 5,5'-bis(2-acylphenyl)diazo-dipyrromethane (H2L) with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 (CuL) and 3 (NIL). The crystal of complex...The reactions of 5,5'-bis(2-acylphenyl)diazo-dipyrromethane (H2L) with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 (CuL) and 3 (NIL). The crystal of complex 2 is of monoclinic system, space group P21 with a = 10.040(5), b = 11.900(5), c = 11.170(5) A, β = 93.057(8)°, V = 1332.8(2) A3, Z = 2, C29H28N602Cu, Mr = 556.11, Dc = 1.386 g/cm, F(000) = 578 and/z(MoKa) = 0.857 mm^-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a = 12.0445(6), b = 17.2101(8), c = 16.3304(6) A, β = 128.407(2)°, V = 2654.6(2) A3, Z = 4, C29H28N6O2Ni, Mr= 551.28, Dc= 1.380 g/cm, F(000) = 1152 and μ(MoKa) = 0.770 mm^-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.展开更多
The title compound, [HgI2(C12H8N4S)], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086(2), b = 6.0365(6), c = ...The title compound, [HgI2(C12H8N4S)], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086(2), b = 6.0365(6), c = 20.286(2)°A,β= 108.818(5)°, V = 1632.7(3)°A^3, Mr = 694.67, Z = 4, D, = 2.826 g/cm^3,μ= 13.331 mm^-1, F(000) = 1240, S = 1.108, the final R = 0.0438 and wR = 0.0934 for 3085 observed reflections (I〉 2σ(I)). The Hg(Ⅱ) atom is coordinated by two 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (L) molecules and two iodine anions in a distorted tetrahedral coordination geometry. Mercury atoms are linked by the organic ligands to form a one-dimensional zigzag chain. It is noteworthy that such 1D zigzag chains are extended into a two-dimensional double layer framework through I…I interactions展开更多
One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characte...One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860(5), b = 13.8246(6), c = 19.0140(8) A, β = 104.3870(1)°, V = 3128.2(2) A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F(000) = 1444 and μ(Mo Kα) = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ(I) and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni(OTP)]n chain and the 2D [Ni2(bib)3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.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
The new title compound (2E,6E)-2,6-bis(2,3-dimethoxybenzylidene)cyclohexanone (C 24 H 26 O 5,M r=394.45) has been synthesized,and its crystal structure was studied.The title compound crystallizes in the orthorho...The new title compound (2E,6E)-2,6-bis(2,3-dimethoxybenzylidene)cyclohexanone (C 24 H 26 O 5,M r=394.45) has been synthesized,and its crystal structure was studied.The title compound crystallizes in the orthorhombic system,space group Pca2 1 with a=17.536(2),b=14.8515(16),c=8.0512(9),V=2096.8(4) 3,Z=4,D c=1.250 g/cm 3,λ=0.71073,μ=0.087 mm-1 and F(000)=840.The structure was solved by direct methods and refined to R=0.0533 and wR=0.1248 from 2727 observed reflections (I 2σ(Ⅰ)).The title molecules are connected through hydrogen bonds to generate a 3-D supramolecule.The preliminary biological tests showed definitely biological activity for the title compound.展开更多
Efficient Mukaiyama-type aldol reaction of 1, 2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported. The resulting succinoylation product of aldehyde was converted into the synthetic...Efficient Mukaiyama-type aldol reaction of 1, 2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported. The resulting succinoylation product of aldehyde was converted into the synthetic useful g-lactone and butenolide derivatives.展开更多
基金financially supported by the National Key R&D Program of China 2021YFC2101604)the National Natural Science Foundation of China(22278339,21978248)+1 种基金the Guangdong Provincial Key Research and Development Program(2020B0101070001)the Natural Science Foundation of Fujian Province of China(2019J06005)。
文摘5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.
基金Supported by the National "973" project (No. 613740102)
文摘2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324(2),b = 0.6454(3),c = 0.7062(3) nm,α= 111.550(4),β= 95.505(4),γ= 113.395(4)°,V = 0.23595(16) nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F(000) = 126,R = 0.0304 and wR = 0.0907.
基金Supported by Indian Council of Medical Research and Department of Biotechnology,Government of India
文摘AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.
基金supported by the research foundation of Hebei University of Science and Technology
文摘An efficient synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.
基金Supported by Nanjing University of Posts and Telecommunications (No. NY209032)the National Natural Science Foundation of China (No. 21001065)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938(3),b = 1.9422(5),c = 0.9406(2) nm,β = 121.891(4)°,V = 2.0066(9) nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ(MoKα) = 4.209 mm?1,F(000) = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ(I).In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.
基金This work was supported by the China Petroleum & Chemical Science and Technology Foundation (No. 205026) the Tianjin Science and Technology Plan Foundation (No. 06TXTJJC14400)
文摘The title compound N,N'-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylene diamine (DPTDEDA, C12H26N2O4P2S2) was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557(16), b = 11.299(12), c = 12.163(13)A,β = 98.707(19)^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ(MoKa) = 0.447 mm^-1, Mr = 388.41, V = 1977(4)A3, F(000) = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections (I 〉 2σ(I)). X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.
基金supported by the research grant of Phytochemistry Key Laboratory of Shaanxi Province (No. 02js40)
文摘The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17~25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ 〉2σ(Ⅰ) were used in the structure solution and refinement.
文摘The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.
基金supported by the National Natural Science Foundation of China (No. 21101097)Natural Science Foundation of Shandong Province (ZR2010BQ023)the State Key Laboratory of Solid Lubrication (No. 0701)
文摘Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)(H2O)4]·3H2O}n (M = Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.
基金supported by the National Natural Science Foundation of China (No. 20702038)
文摘3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)pyrrol-2-yl)pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·(CH3OH)2, belongs to the orthorhombic system, space group Pccn with a = 18.094(2), b = 11.6890(16), c = 13.3629(19) , V = 2826.3(7) 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F(000) = 1080 and μ(MoKα) = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ(I), and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.
文摘A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of iodine and 1,4- bis(triphenylphosphonium)-2-butene peroxodisulfate.
基金supported by the Foundation of State Key Laboratory of Coal Conversion(No.J17-18-611)the National Natural Science Foundation of China(No.21676258)
文摘Two novel zinc(Ⅱ) coordination polymers, [Zn2(BCB)(CH3OH)(μ3-OH)]n(1) and {[Zn2(BCB)(μ3-OH)(H2O)2]·CH3OH}n (2), have been constructed from 3,5-bis(2-carboxylphenoxy)benzoic acid(H3BCB) and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn4(COO)4(μ3-OH)2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.
基金supported by the National Natural Science Foundation of China(NSFC No.21172174)Program of Study Abroad for Young Scholar sponsored by Tianjin Municipal Education Commission
文摘The reactions of 5,5'-bis(2-acylphenyl)diazo-dipyrromethane (H2L) with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 (CuL) and 3 (NIL). The crystal of complex 2 is of monoclinic system, space group P21 with a = 10.040(5), b = 11.900(5), c = 11.170(5) A, β = 93.057(8)°, V = 1332.8(2) A3, Z = 2, C29H28N602Cu, Mr = 556.11, Dc = 1.386 g/cm, F(000) = 578 and/z(MoKa) = 0.857 mm^-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a = 12.0445(6), b = 17.2101(8), c = 16.3304(6) A, β = 128.407(2)°, V = 2654.6(2) A3, Z = 4, C29H28N6O2Ni, Mr= 551.28, Dc= 1.380 g/cm, F(000) = 1152 and μ(MoKa) = 0.770 mm^-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.
基金This work was supported by the 973 Program of the MOST (001CB108906) and the Natural Science Foundation of Fujian Province (2005HZ01-1)
文摘The title compound, [HgI2(C12H8N4S)], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086(2), b = 6.0365(6), c = 20.286(2)°A,β= 108.818(5)°, V = 1632.7(3)°A^3, Mr = 694.67, Z = 4, D, = 2.826 g/cm^3,μ= 13.331 mm^-1, F(000) = 1240, S = 1.108, the final R = 0.0438 and wR = 0.0934 for 3085 observed reflections (I〉 2σ(I)). The Hg(Ⅱ) atom is coordinated by two 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (L) molecules and two iodine anions in a distorted tetrahedral coordination geometry. Mercury atoms are linked by the organic ligands to form a one-dimensional zigzag chain. It is noteworthy that such 1D zigzag chains are extended into a two-dimensional double layer framework through I…I interactions
基金supported by the Natural Science Foundation of Shandong Province(ZR2011BL020,ZR2012CM019)National Natural Science Foundation of China(21451001)Key Discipline and Innovation Team of Qilu Normal University
文摘One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860(5), b = 13.8246(6), c = 19.0140(8) A, β = 104.3870(1)°, V = 3128.2(2) A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F(000) = 1444 and μ(Mo Kα) = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ(I) and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni(OTP)]n chain and the 2D [Ni2(bib)3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.
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 (81072683)Project of Wenzhou Sci & Tech Bureau (Y20100006)Natural Science Foundation of Zhejiang Province (Y20101108)
文摘The new title compound (2E,6E)-2,6-bis(2,3-dimethoxybenzylidene)cyclohexanone (C 24 H 26 O 5,M r=394.45) has been synthesized,and its crystal structure was studied.The title compound crystallizes in the orthorhombic system,space group Pca2 1 with a=17.536(2),b=14.8515(16),c=8.0512(9),V=2096.8(4) 3,Z=4,D c=1.250 g/cm 3,λ=0.71073,μ=0.087 mm-1 and F(000)=840.The structure was solved by direct methods and refined to R=0.0533 and wR=0.1248 from 2727 observed reflections (I 2σ(Ⅰ)).The title molecules are connected through hydrogen bonds to generate a 3-D supramolecule.The preliminary biological tests showed definitely biological activity for the title compound.
基金We are grateful for the financial supports from the National Outstanding Youth Fund (No. 29925204) the Foundation for University Key Teacher by the Ministry of Education of China and a Visiting Fund of the National Laboratory of Applied Organic Chem
文摘Efficient Mukaiyama-type aldol reaction of 1, 2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported. The resulting succinoylation product of aldehyde was converted into the synthetic useful g-lactone and butenolide derivatives.