Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characteri...Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321（7）, b = 11.781（0）, c = 15.593（2） A, fl = 110.273（6）°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F（000） = 1312, Dc = 1.415 g/cm3,μ（MoKa） = 1.004 mm＂1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20（/）. Complex 2 is of monoclinic system, space group C2/c with a = 16.7767（2）, b = 10.8989（2）, c = 17.4928（2） A, fl = 90.614（9）°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F（000） = 1528, Dc = 1.568 g＇cm^-3, μ（MoKa） = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ（I）. The two complexes were formed by Schiff base 2-methoxy-6-（phenyliminiomethyl） phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.展开更多
Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other ...Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.展开更多
（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LL...（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.展开更多
The neodymium chloride complex[Nd（ONN＇O）Cl（THF）]2 supported by amine-bis（phenolate） ligand was synthesized by the metathesis reaction of anhydrous NdCl3 with Li2（ONN＇O）[H2ONN＇O = Me2NCH2CH2N（CH2-3-Bu2^t-5-...The neodymium chloride complex[Nd（ONN＇O）Cl（THF）]2 supported by amine-bis（phenolate） ligand was synthesized by the metathesis reaction of anhydrous NdCl3 with Li2（ONN＇O）[H2ONN＇O = Me2NCH2CH2N（CH2-3-Bu2^t-5-Me-C6H2OH）2]in high yield.X-ray structural determination shows[Nd（ONN＇O）Cl（THF）]2 complex consists of two seven-coordinate neodymium centers linked throughμ-Cl bridges.And this complex was successfully used to initiate the ring-opening polymerization（ROP） ofε-caprolactone.展开更多
A series of rare-earth(RE)metal complexes[RE=La(1,5,6),Nd(2),Sm(3),Y(4)]bearing polydentate N’-(2-aminoethyl)-N,N-dimethyl-1,2-ethylenediamine bridged-tris(phenolto)ligands were synthesized and characterized.The acti...A series of rare-earth(RE)metal complexes[RE=La(1,5,6),Nd(2),Sm(3),Y(4)]bearing polydentate N’-(2-aminoethyl)-N,N-dimethyl-1,2-ethylenediamine bridged-tris(phenolto)ligands were synthesized and characterized.The activity of complexes 1-6 for catalysing the cycloaddition reaction of CO_(2) and epoxides was studied,and the lanthanum complex 1 showed the highest activity.Under the conditions of 1 bar CO_(2) and 25℃,lanthanum complex 1 catalysed the reaction of 18 mono-substituted epoxides,generating cyclic carbonates in 50-99% yields.More importantly,it also catalysed reactions of 6 di-substituted epoxides under ambient conditions(1 bar CO_(2) and 25℃),and generated cyclic carbonates in 85-99% yields.This lanthanum complex is the first catalyst capable of converting di-substituted epoxides into internal cyclic carbonates under ambient conditions.Kinetic study was conducted to determine rate orders and Gibbs activation energy.A DFT study proved that poly(phenolto)ligands play vital roles in product dissociation.展开更多
A new kind of inorganic polymer, viz, silica-supported polytitazane (Ti-N), and its platinum complex (Ti-N-Pt) were prepared. Cyclohexanone can be obtained in a maximum yield of about 62.2% in the hydrogenation of phe...A new kind of inorganic polymer, viz, silica-supported polytitazane (Ti-N), and its platinum complex (Ti-N-Pt) were prepared. Cyclohexanone can be obtained in a maximum yield of about 62.2% in the hydrogenation of phenol over Ti-N-Pt at room temperature under atmospheric pressure. The effects of mole ratio of N/Pt in the complex, concentration of the catalyst and reaction temperature on the catalytic activity and selectivity have been studied. The complex can be reused several times without loss in its catalytic activity.展开更多
Objective To isolate, incubate, and identify 4-chlorophenol-degrading complex bacteria, determine the tolerance of these bacteria to phenolic derivatives and study their synergetic metabolism as well as the aboriginal...Objective To isolate, incubate, and identify 4-chlorophenol-degrading complex bacteria, determine the tolerance of these bacteria to phenolic derivatives and study their synergetic metabolism as well as the aboriginal microbes and co-metabolic degradation of mixed chlorophenols in river water. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicants. Biodegradability of phenolic derivatives was determined by adding 4-chlorophenol-degrading bacteria in river water. Results The complex bacteria were identified as Mycopiana, Alcaligenes, Pseudomonas, and Flavobacterium. The domesticated complex bacteria were more tolerant to phenolic derivatives than the aboriginal bacteria from Qinhuai River. The biodegradability of chlorophenols, dihydroxybenzenes and nitrophenols under various aquatic conditions was determined and compared. The complex bacteria exhibited a higher metabolic efficiency on chemicals than the aboriginal microbes, and the final removal rate of phenolic derivatives was increased at least by 55% when the complex bacteria were added into river water. The metabolic relationship between dominant mixed bacteria and river bacteria was studied. Conclusion The complex bacteria domesticated by 4-chlorophenol can grow and be metabolized to take other chlorophenols, dihydroxybenzenes and nitrophenols as the sole carbon and energy source. There is a synergetic metabolism of most compounds between the aboriginal microbes in river water and the domesticated complex bacteria, 4- chlorophenol-degrading bacteria can co-metabolize various chlorophenols in fiver water.展开更多
A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% select...A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.展开更多
ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder s...ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.展开更多
A novel pyridine-phenol boron complex[（dppy）BF] was encapsulated into polymer/silica composite matrix by sol-gel process. UV-Vis absorption spectra show that this process can control the aggregation structure of com...A novel pyridine-phenol boron complex[（dppy）BF] was encapsulated into polymer/silica composite matrix by sol-gel process. UV-Vis absorption spectra show that this process can control the aggregation structure of complex （dppy）BF. The results of photoluminescence of （dppy）BF in sol-gel composite film indicate that both fluorescence intensity and photostability are markedly increased using this method compared with other methods, which increases the practical significance of such composite film.展开更多
A series of binuclear lanthanide complexes with formulas[Dy_(2)(DMOMP)_(2)(TFNB)_(4)]·CH_(3)CH_(2)OCH_(2)CH_(3)(1),[Dy_(2)(DMOEP)_(2)(TFNB)_(4)](2),[Dy_(2)(DMOEP)_(2)(BTFA)_(4)](3),[Dy_(2)(DMOEP)_(2)(TTA)_(4)](4)...A series of binuclear lanthanide complexes with formulas[Dy_(2)(DMOMP)_(2)(TFNB)_(4)]·CH_(3)CH_(2)OCH_(2)CH_(3)(1),[Dy_(2)(DMOEP)_(2)(TFNB)_(4)](2),[Dy_(2)(DMOEP)_(2)(BTFA)_(4)](3),[Dy_(2)(DMOEP)_(2)(TTA)_(4)](4),and[Dy_(2)(DMOAP)_(2)(TFNB)_(4)](5),(DMOMP=2,6-dimethoxy-4-methylphenol,DMOEP=methyl 3,5-dimethoxy-4-hydroxybenzoate,DMOAP=3,5-dimethoxy-4-hydroxybenzaldehyde,TFNB=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione,BTFA=benzoyltrifluoroacetone,TTA=2-thenoyltrifluoroacetone)were structurally and magnetically characterized.The core structures of these complexes consist of dinuclear lanthanide(Ⅲ)ions bridged firmly by phenoxyl O atoms from two nearly horizontal and isolated 2,6-dimethoxyphenol(DMOP)derivatives,which provide an ideal model to investigate the synergistic contribution of single-ion anisotropy and magnetic exchange interaction.展开更多
A potential tetradentate monoanionic N_(2)O_(2) chelator,HL,derived from the condensation of o-vanillin and N,N-dimethylethylenediammine,has been reacted with nickel perchlorate and sodium azide to yield the dinuclear...A potential tetradentate monoanionic N_(2)O_(2) chelator,HL,derived from the condensation of o-vanillin and N,N-dimethylethylenediammine,has been reacted with nickel perchlorate and sodium azide to yield the dinuclear Ni(Ⅱ)complex[Ni(L)(μ_(1,1)-N_(3))Ni(L)(OH_(2))_(2)]·ClO_(4)(1),where L=Me_(2)N(CH_(2))_(2)NvCH-C_(6)H_(3)(O^(-))-(OCH_(3)).The complex has been characterized by X-ray diffraction analysis and different spectroscopic techniques.The coordination geometry around the Ni(II)centres is a distorted octahedron,with the azide ligand and the phenolato oxygen atom bridging inμ1,1 andμ2 mode,respectively.The EPR spectra,recorded at liquid nitrogen temperature(77 K)and room temperature(298 K),show g factors of 2.080 and 2.085,in agreement with the structure determined by X-ray diffraction analysis.The VTM study confirms that there are ferromagnetic interactions between the bridging binuclear Ni(II)ions(S=1).The evaluation of cytotoxic effects on different human cancer cell lines(A-549,MCF-7 and CaCo-2)suggests that both the ligand and complex 1 have potential anticancer properties.Furthermore,they also exhibit anti-mycobacterial activity against M.tuberculosis H37Rv(ATCC 27294)and M.tuberculosis H37Ra(ATCC 25177)strains.Molecular docking of HL with the enoyl acyl carrier protein reductase of M.tuberculosis H37R_(v)(PDB ID:4U0K)has been examined,showing that HL forms two hydrogen bonds with Lys165(1.94 and 2.53A)in its best docked pose.展开更多
Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydr...Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD: while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.展开更多
Jasmonic acid(JA)signaling pathway plays an important role in tanshinone and phenolic acid biosynthesis in Salvia miltiorrhiza.However,the specific regulatory mechanism remains largely unclear.Previous work showed tha...Jasmonic acid(JA)signaling pathway plays an important role in tanshinone and phenolic acid biosynthesis in Salvia miltiorrhiza.However,the specific regulatory mechanism remains largely unclear.Previous work showed that a JASMONATE ZIM-domain(JAZ)protein,SmJAZ9,acted as a repressor of tanshinone production in S.miltiorrhiza.In this study,we revealed that SmJAZ9 reduced both phenolic acid accumulation and related biosynthetic gene expression,confirming that SmJAZ9 also negatively affected phenolic acid biosynthesis.Then,we identified a novel MYB transcription factor,SmMYB76,which interacted with SmJAZ9.SmMYB76 repressed phenolic acid biosynthesis by directly downregulating SmPAL1,Sm4CL2,and SmRAS1.Further investigation demonstrated that JA mediated phenolic acids biosynthesis via SmJAZ9-SmMYB76 complex.Taken together,these findings state the molecular mechanism that SmJAZ9-SmMYB76 regulated phenolic acid biosynthesis at the transcriptional and protein levels,which provided new insights into JA signaling pathway regulating plant metabolism.展开更多
Herein,we report the application of four amino-tris(phenolate)-based metal complexes incorporating Ti(IV)or Zr(IV)centres(2a-3b)as homogeneous catalysts for the conversion of CO_(2)and epoxides into cyclic carbonates....Herein,we report the application of four amino-tris(phenolate)-based metal complexes incorporating Ti(IV)or Zr(IV)centres(2a-3b)as homogeneous catalysts for the conversion of CO_(2)and epoxides into cyclic carbonates.The four complexes were synthesised,characterised and then evaluated in combination with tetrabutylammo-nium iodide,bromide or chloride as binary catalytic systems for the reaction of CO_(2)with 1,2-epoxyhexane as epoxide substrate at 12 bar CO_(2)pressure and 90?C for 2 h.The catalytic systems comprising the two Ti(IV)complexes(2a and 2b)showed similar performance.One notable exception was the catalytic system consisting of titanium complex 2b,bearing an axial Cl-ligand,and tetrabutylammonium chloride,which displayed higher catalytic activity compared to other titanium-based systems.Even higher activity was achieved with Zr(IV)complex 3a,bearing an axial isopropoxide ligand,which reached turnover numbers(TON metal)up to 1920 for the reaction of CO_(2)with 1,2-epoxyhexane at 12 bar CO_(2)pressure and 90?C for 2 h.This performance is comparable with that of state-of-the-art catalysts for this reaction.The catalytic system consisting of complex 3a and tetra-butylammonium bromide was explored further by investigating its applicability with a broad substrate scope,achieving quantitative conversion of several epoxides with CO_(2)into cyclic carbonate products at 90?C and 12 bar CO_(2)pressure for 18 h.The selectivity towards the cyclic carbonate products was?98%for all studied terminal epoxides and?80%for all examined cyclohexene-type epoxides.展开更多
The widespread application of phenolic substances in the field of food,medicine and industry,is harmful to the environment and human health.Therefore,it is very important to develop a con-venient and effective method ...The widespread application of phenolic substances in the field of food,medicine and industry,is harmful to the environment and human health.Therefore,it is very important to develop a con-venient and effective method to detect and degrade phenolic compounds.Herein,we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition,{[Cu(dap)(3-PA)]4(SiW_(12)O_(40))(H_(2)O)_(2)}·2H_(2)O(1,dap=1,2-diaminopropane,3-HPA=3-pyridineacrylic acid).1 shows an interesting 1D ladder-like structure.As a bifunctional catalyst,1 can be employed as a colori-metric sensor toward phenol with the relatively low detection limit(LOD)of 0.36μmol/L(S/N=3)in the wide range(0.001-0.1 mmol/L).The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%-105%.In addition,1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96%for 100 min and wide pH universality.The selectivity,stability and reliability of the detection of 1 towards phenol,as well as the detection for 4-chlorophenol,o-cresol,4-nitrophenol and phloroglucinol were stud-ied.Furthermore,the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.展开更多
As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalentl...As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures ofthe new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical andphotochemical properties were also studied.展开更多
The zinc（Ⅱ） complex with Hpbx （Hpbx = 2-（benzoxazol-2-yl）phenol） and Hpbm （Hpbm = 2-（benzimidazol-2-yl）phenol）, namely [Zn（pbm）2]1.633[Zn（pbx）212.367·DMF·2H2O 1, has been synthesized and chara...The zinc（Ⅱ） complex with Hpbx （Hpbx = 2-（benzoxazol-2-yl）phenol） and Hpbm （Hpbm = 2-（benzimidazol-2-yl）phenol）, namely [Zn（pbm）2]1.633[Zn（pbx）212.367·DMF·2H2O 1, has been synthesized and characterized by X-ray crystallography, FTIR and elemental analysis. The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn（pbm）2] and [Zn（pbx）2] with the ratio of ca. 0.408/0.592. Solvate water and DMF molecules are also present in the lattice. Crystal data for 1; monoclinic, space group P21/c, Mr= 2049.02, Z = 2, α = 9.7571（6）, b = 25.6415（16）, c = 19.8675（10） A, β= 111.342（2）°, V = 4629.7（5） A^3, Dc = 1.470 g/cm^3,μ = 1.100 mm^-1, F（000） = 2104, R = 0.0575 and wR = 0.1282 for 5528 observed reflections （I〉2σ（I））. The photoluminescent spectra for this compound have also been studied.展开更多
基金supported by the Natural Science Foundation of Zhejiang Province (LY12B01003)
文摘Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321（7）, b = 11.781（0）, c = 15.593（2） A, fl = 110.273（6）°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F（000） = 1312, Dc = 1.415 g/cm3,μ（MoKa） = 1.004 mm＂1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20（/）. Complex 2 is of monoclinic system, space group C2/c with a = 16.7767（2）, b = 10.8989（2）, c = 17.4928（2） A, fl = 90.614（9）°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F（000） = 1528, Dc = 1.568 g＇cm^-3, μ（MoKa） = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ（I）. The two complexes were formed by Schiff base 2-methoxy-6-（phenyliminiomethyl） phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.
文摘Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.
基金Project supported by the National Natural Science Foundation of China (20472063)the Key Laboratory of Organic Synthesis of Jiangsu Province
文摘（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.
基金the financial supports of the National Natural Science Foundation of China (No.20774078)the Special Funds for Major Basic Research Projects(No.2005CB623802)Scientific Research Foundation for Returned Scholars,Ministry of Education of China
文摘The neodymium chloride complex[Nd（ONN＇O）Cl（THF）]2 supported by amine-bis（phenolate） ligand was synthesized by the metathesis reaction of anhydrous NdCl3 with Li2（ONN＇O）[H2ONN＇O = Me2NCH2CH2N（CH2-3-Bu2^t-5-Me-C6H2OH）2]in high yield.X-ray structural determination shows[Nd（ONN＇O）Cl（THF）]2 complex consists of two seven-coordinate neodymium centers linked throughμ-Cl bridges.And this complex was successfully used to initiate the ring-opening polymerization（ROP） ofε-caprolactone.
基金the National Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005,19KJA320007)PAPD.
文摘A series of rare-earth(RE)metal complexes[RE=La(1,5,6),Nd(2),Sm(3),Y(4)]bearing polydentate N’-(2-aminoethyl)-N,N-dimethyl-1,2-ethylenediamine bridged-tris(phenolto)ligands were synthesized and characterized.The activity of complexes 1-6 for catalysing the cycloaddition reaction of CO_(2) and epoxides was studied,and the lanthanum complex 1 showed the highest activity.Under the conditions of 1 bar CO_(2) and 25℃,lanthanum complex 1 catalysed the reaction of 18 mono-substituted epoxides,generating cyclic carbonates in 50-99% yields.More importantly,it also catalysed reactions of 6 di-substituted epoxides under ambient conditions(1 bar CO_(2) and 25℃),and generated cyclic carbonates in 85-99% yields.This lanthanum complex is the first catalyst capable of converting di-substituted epoxides into internal cyclic carbonates under ambient conditions.Kinetic study was conducted to determine rate orders and Gibbs activation energy.A DFT study proved that poly(phenolto)ligands play vital roles in product dissociation.
文摘A new kind of inorganic polymer, viz, silica-supported polytitazane (Ti-N), and its platinum complex (Ti-N-Pt) were prepared. Cyclohexanone can be obtained in a maximum yield of about 62.2% in the hydrogenation of phenol over Ti-N-Pt at room temperature under atmospheric pressure. The effects of mole ratio of N/Pt in the complex, concentration of the catalyst and reaction temperature on the catalytic activity and selectivity have been studied. The complex can be reused several times without loss in its catalytic activity.
基金supported by 973 Program (No. 2008CB418203)New Century Excellent Talents in University (No. 05-0481)
文摘Objective To isolate, incubate, and identify 4-chlorophenol-degrading complex bacteria, determine the tolerance of these bacteria to phenolic derivatives and study their synergetic metabolism as well as the aboriginal microbes and co-metabolic degradation of mixed chlorophenols in river water. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicants. Biodegradability of phenolic derivatives was determined by adding 4-chlorophenol-degrading bacteria in river water. Results The complex bacteria were identified as Mycopiana, Alcaligenes, Pseudomonas, and Flavobacterium. The domesticated complex bacteria were more tolerant to phenolic derivatives than the aboriginal bacteria from Qinhuai River. The biodegradability of chlorophenols, dihydroxybenzenes and nitrophenols under various aquatic conditions was determined and compared. The complex bacteria exhibited a higher metabolic efficiency on chemicals than the aboriginal microbes, and the final removal rate of phenolic derivatives was increased at least by 55% when the complex bacteria were added into river water. The metabolic relationship between dominant mixed bacteria and river bacteria was studied. Conclusion The complex bacteria domesticated by 4-chlorophenol can grow and be metabolized to take other chlorophenols, dihydroxybenzenes and nitrophenols as the sole carbon and energy source. There is a synergetic metabolism of most compounds between the aboriginal microbes in river water and the domesticated complex bacteria, 4- chlorophenol-degrading bacteria can co-metabolize various chlorophenols in fiver water.
文摘A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.
文摘ESR and IR measurements have been carried out for a copper(Ⅱ)complex of phenolic polymeric crown ether,As a result,the triplet ESR spectrum(S=1)of 3d_z2 ground state copper(Ⅱ)ions was first observed for the powder sample.It indicated that there existed intramolecular spin-spin interaction betweeen 3d_Z2 ground state copper(Ⅱ)and copper(Ⅱ)ions.In this binuclear triplet cluster,the axial ligntion of one water molecule in a sandwich position to two adjacent copper(Ⅱ) ions was also confirmed by IR spectra,All things considered,a possible structure for the complex was proposed.
基金Supported by the National Basic Research Program of China(No2007CB80800)
文摘A novel pyridine-phenol boron complex[（dppy）BF] was encapsulated into polymer/silica composite matrix by sol-gel process. UV-Vis absorption spectra show that this process can control the aggregation structure of complex （dppy）BF. The results of photoluminescence of （dppy）BF in sol-gel composite film indicate that both fluorescence intensity and photostability are markedly increased using this method compared with other methods, which increases the practical significance of such composite film.
基金supported by the NSFC(No.21572048,21102039)the Educational Commission of Heilongjiang Province(LH2019B016)the Heilongjiang University(JCL201605,2017230101001473).
文摘A series of binuclear lanthanide complexes with formulas[Dy_(2)(DMOMP)_(2)(TFNB)_(4)]·CH_(3)CH_(2)OCH_(2)CH_(3)(1),[Dy_(2)(DMOEP)_(2)(TFNB)_(4)](2),[Dy_(2)(DMOEP)_(2)(BTFA)_(4)](3),[Dy_(2)(DMOEP)_(2)(TTA)_(4)](4),and[Dy_(2)(DMOAP)_(2)(TFNB)_(4)](5),(DMOMP=2,6-dimethoxy-4-methylphenol,DMOEP=methyl 3,5-dimethoxy-4-hydroxybenzoate,DMOAP=3,5-dimethoxy-4-hydroxybenzaldehyde,TFNB=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione,BTFA=benzoyltrifluoroacetone,TTA=2-thenoyltrifluoroacetone)were structurally and magnetically characterized.The core structures of these complexes consist of dinuclear lanthanide(Ⅲ)ions bridged firmly by phenoxyl O atoms from two nearly horizontal and isolated 2,6-dimethoxyphenol(DMOP)derivatives,which provide an ideal model to investigate the synergistic contribution of single-ion anisotropy and magnetic exchange interaction.
基金West Bengal DST,Kolkata,India for the grant(228/1(10)/(Sanc.)/ST/P/S&T/9G-16/2012).
文摘A potential tetradentate monoanionic N_(2)O_(2) chelator,HL,derived from the condensation of o-vanillin and N,N-dimethylethylenediammine,has been reacted with nickel perchlorate and sodium azide to yield the dinuclear Ni(Ⅱ)complex[Ni(L)(μ_(1,1)-N_(3))Ni(L)(OH_(2))_(2)]·ClO_(4)(1),where L=Me_(2)N(CH_(2))_(2)NvCH-C_(6)H_(3)(O^(-))-(OCH_(3)).The complex has been characterized by X-ray diffraction analysis and different spectroscopic techniques.The coordination geometry around the Ni(II)centres is a distorted octahedron,with the azide ligand and the phenolato oxygen atom bridging inμ1,1 andμ2 mode,respectively.The EPR spectra,recorded at liquid nitrogen temperature(77 K)and room temperature(298 K),show g factors of 2.080 and 2.085,in agreement with the structure determined by X-ray diffraction analysis.The VTM study confirms that there are ferromagnetic interactions between the bridging binuclear Ni(II)ions(S=1).The evaluation of cytotoxic effects on different human cancer cell lines(A-549,MCF-7 and CaCo-2)suggests that both the ligand and complex 1 have potential anticancer properties.Furthermore,they also exhibit anti-mycobacterial activity against M.tuberculosis H37Rv(ATCC 27294)and M.tuberculosis H37Ra(ATCC 25177)strains.Molecular docking of HL with the enoyl acyl carrier protein reductase of M.tuberculosis H37R_(v)(PDB ID:4U0K)has been examined,showing that HL forms two hydrogen bonds with Lys165(1.94 and 2.53A)in its best docked pose.
文摘Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD: while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.
基金supported by the National Natural Science Foundation of China(82073963,81522049)The Key Science and Technology Projects of Breeding New Varieties of Agriculture in Zhejiang Province(2021C02074-3)+2 种基金Zhejiang Provincial Ten Thousands Program for Leading Talents of Science and Technology Innovation(2018R52050)Zhejiang Provincial Program for the Cultivation of High-level Innovative Health Talentsthe Research Project of Zhejiang Chinese Medical University(2021JKZDZC06).
文摘Jasmonic acid(JA)signaling pathway plays an important role in tanshinone and phenolic acid biosynthesis in Salvia miltiorrhiza.However,the specific regulatory mechanism remains largely unclear.Previous work showed that a JASMONATE ZIM-domain(JAZ)protein,SmJAZ9,acted as a repressor of tanshinone production in S.miltiorrhiza.In this study,we revealed that SmJAZ9 reduced both phenolic acid accumulation and related biosynthetic gene expression,confirming that SmJAZ9 also negatively affected phenolic acid biosynthesis.Then,we identified a novel MYB transcription factor,SmMYB76,which interacted with SmJAZ9.SmMYB76 repressed phenolic acid biosynthesis by directly downregulating SmPAL1,Sm4CL2,and SmRAS1.Further investigation demonstrated that JA mediated phenolic acids biosynthesis via SmJAZ9-SmMYB76 complex.Taken together,these findings state the molecular mechanism that SmJAZ9-SmMYB76 regulated phenolic acid biosynthesis at the transcriptional and protein levels,which provided new insights into JA signaling pathway regulating plant metabolism.
文摘Herein,we report the application of four amino-tris(phenolate)-based metal complexes incorporating Ti(IV)or Zr(IV)centres(2a-3b)as homogeneous catalysts for the conversion of CO_(2)and epoxides into cyclic carbonates.The four complexes were synthesised,characterised and then evaluated in combination with tetrabutylammo-nium iodide,bromide or chloride as binary catalytic systems for the reaction of CO_(2)with 1,2-epoxyhexane as epoxide substrate at 12 bar CO_(2)pressure and 90?C for 2 h.The catalytic systems comprising the two Ti(IV)complexes(2a and 2b)showed similar performance.One notable exception was the catalytic system consisting of titanium complex 2b,bearing an axial Cl-ligand,and tetrabutylammonium chloride,which displayed higher catalytic activity compared to other titanium-based systems.Even higher activity was achieved with Zr(IV)complex 3a,bearing an axial isopropoxide ligand,which reached turnover numbers(TON metal)up to 1920 for the reaction of CO_(2)with 1,2-epoxyhexane at 12 bar CO_(2)pressure and 90?C for 2 h.This performance is comparable with that of state-of-the-art catalysts for this reaction.The catalytic system consisting of complex 3a and tetra-butylammonium bromide was explored further by investigating its applicability with a broad substrate scope,achieving quantitative conversion of several epoxides with CO_(2)into cyclic carbonate products at 90?C and 12 bar CO_(2)pressure for 18 h.The selectivity towards the cyclic carbonate products was?98%for all studied terminal epoxides and?80%for all examined cyclohexene-type epoxides.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.21901018,21971024,22271021)the Natural Science Foundation and Education Department of Liaoning province(Nos.2022-MS-373,2021-MS-312,LJ2020008).
文摘The widespread application of phenolic substances in the field of food,medicine and industry,is harmful to the environment and human health.Therefore,it is very important to develop a con-venient and effective method to detect and degrade phenolic compounds.Herein,we report a new keggin-type polyoxometallate-based metal-organic complex self-assembled under solvothermal condition,{[Cu(dap)(3-PA)]4(SiW_(12)O_(40))(H_(2)O)_(2)}·2H_(2)O(1,dap=1,2-diaminopropane,3-HPA=3-pyridineacrylic acid).1 shows an interesting 1D ladder-like structure.As a bifunctional catalyst,1 can be employed as a colori-metric sensor toward phenol with the relatively low detection limit(LOD)of 0.36μmol/L(S/N=3)in the wide range(0.001-0.1 mmol/L).The title colorimetric sensor is applied to determine phenol in various water environment with good recoveries ranging from 95%-105%.In addition,1 also exhibits excellent photocatalytic degradation toward phenol under visible light with the highest removal efficiency at 96%for 100 min and wide pH universality.The selectivity,stability and reliability of the detection of 1 towards phenol,as well as the detection for 4-chlorophenol,o-cresol,4-nitrophenol and phloroglucinol were stud-ied.Furthermore,the photocatalytic reaction kinetics and the mechanisms of photodegradation of phenol were also investigated in detail.
文摘As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures ofthe new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical andphotochemical properties were also studied.
基金This work was supported by the Natural Science Foundation of Guangdong Province (No. 06301028)
文摘The zinc（Ⅱ） complex with Hpbx （Hpbx = 2-（benzoxazol-2-yl）phenol） and Hpbm （Hpbm = 2-（benzimidazol-2-yl）phenol）, namely [Zn（pbm）2]1.633[Zn（pbx）212.367·DMF·2H2O 1, has been synthesized and characterized by X-ray crystallography, FTIR and elemental analysis. The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn（pbm）2] and [Zn（pbx）2] with the ratio of ca. 0.408/0.592. Solvate water and DMF molecules are also present in the lattice. Crystal data for 1; monoclinic, space group P21/c, Mr= 2049.02, Z = 2, α = 9.7571（6）, b = 25.6415（16）, c = 19.8675（10） A, β= 111.342（2）°, V = 4629.7（5） A^3, Dc = 1.470 g/cm^3,μ = 1.100 mm^-1, F（000） = 2104, R = 0.0575 and wR = 0.1282 for 5528 observed reflections （I〉2σ（I））. The photoluminescent spectra for this compound have also been studied.
