A variety of gold（Ⅲ） adducts having a-ligated oxygen-donor ligands have been prepared from [Au（ppy）Cl2]（ppy.phenylpyridine）（1） either by partial or total replacement of the chloride ions. The new species comp...A variety of gold（Ⅲ） adducts having a-ligated oxygen-donor ligands have been prepared from [Au（ppy）Cl2]（ppy.phenylpyridine）（1） either by partial or total replacement of the chloride ions. The new species comprise hydroxo-[Au（ppy）（OH）Cl]（2）, and [Au（ppy）（OH）2]（3）, oxo-[Au2（ppy）2（μ-O）2]（4）, acetate-[Au（ppy）（O2CMe2）] （5）, and alkoxo complexes-[Au（ppy）（OR）Cl]（6, 7） and [Au（ppy）（OR）2]（8--10）（R=Me, 6 and 8; Et, 7 and 9; Pr, 10）. The dihydroxo and the oxo complexes can be interconverted by refluxing the former in anhydrous THF and the latter in water. The hydroxides 2 and 3 and the acetato complex 5 undergo σ-ligand metathesis in ROH solution（R=Me, Et or Pr） to give the corresponding alkoxides.展开更多
The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for futur...The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for future drug design.New Au(Ⅲ)nanosized complexes of cefotaxime(ceph-3)and cefepime(ceph-4)ligands as a 3rd and 4th of cephalosporin generation drugs were synthesized.Gold(Ⅲ)complexes were discussed based on the elemental,molar conductance,thermal and magnetic moment measurements as well as spectral(FTIR,1HNMR,UV-Vis,and XRD)techniques.FT-IR spectra revealed that the ceph-3 and ceph-4 ligands reacted as a bidentate ligands through carboxylate oxygen andβ-lactam oxygen groups.The analytical analysis confirm that the molar ratio is 1∶1(Au 3+/ceph)with general formula[Au(L)(Cl)2]where L=ceph-3 or ceph-4.The structures of Au(Ⅲ)complexes were presence as a square planar geometry.X-ray diffraction patterns referred to a crystalline nature for all synthesized complexes.TEM analyses confirmed that the synthetic gold(Ⅲ)complexes have a nanosized particles.In vitro antimicrobial activities of Au(Ⅲ)complexes were evaluated towards two types of bacteria(G+&G-).The antitumor activities of gold(Ⅲ)complexes are appraised against breast(MCF-7)and colorectal adenocarcinoma(Caco-2)cell lines,which means that the two complexes may consider promising anticancer drugs.展开更多
The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The...The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).展开更多
Thermodynamic properties and electrochemical behaviors of gold and its associated elements, such as silver, copper, nickel and iron, in various complex agent solutions were studied. Within CS（NH2）2, S2O2-3 and SCN- ...Thermodynamic properties and electrochemical behaviors of gold and its associated elements, such as silver, copper, nickel and iron, in various complex agent solutions were studied. Within CS（NH2）2, S2O2-3 and SCN- systems, alkaline thiourea is the optimal nontoxic lixiviating agent substituting cyanide from the viewpoint of thermodynamics. The electrochemical study indicates that the anodic dissolution current densities of gold are 2.616, （1.805,） 1.267, 1.088, 0.556, and 0.145 mA·cm-2 respectively in the solutions of cyanide, alkaline thiourea containing Na2SiO3, SCN-, acidic thiourea, alkaline thiourea and thiosulfate at the potential of 0.500 V. Comparing various lixiviating agents, the alkaline thiourea solution containing Na2SiO3 is of prominent selectivity in leaching gold, in the potential range from 0.500 to 0.600 V, which is most efficient for leaching gold selectively instead of cyanide. The effect on leaching gold is similar to that in the cyanide system.展开更多
A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these c...A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.展开更多
Gold complexes have emerged as promising anticancer metallodrugs due to their efficient thioredoxin reductase(TrxR)inhibition,which disturbs the redox balance of cancer cells.However,in this model,the role of the liga...Gold complexes have emerged as promising anticancer metallodrugs due to their efficient thioredoxin reductase(TrxR)inhibition,which disturbs the redox balance of cancer cells.However,in this model,the role of the ligand(s)coordinated to gold is often overlooked.In this work,we present a series of tetrapyridyl Au(Ⅲ)complexes that exhibit thiol-induced release of a Au(Ⅰ)ion and a tetrapyridyl ligand.The formation of a free Au(Ⅰ)center is responsible for the expected TrxR inhibition.Additionally,the released ligand,which was visible in cells due to its intense blue fluorescence,showed excellent binding properties to the hERG potassium channel.Moreover,these ligands ended up in the lysosomes,resulting in significant lysosome damage.Altogether,the Au(Ⅲ)complexes presented in this work showed broad-spectrum anticancer properties,both in hypoxic 2D monolayers and 3D tumor spheroids.We suggest that the interaction of the released Au(Ⅰ)center and the tetrapyridyl ligand with two different protein targets may combine into prodrugs that overcome hypoxia-induced drug deactivation.展开更多
A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.95...A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.展开更多
Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of...Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.展开更多
The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (...The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓展开更多
A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elem...A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].展开更多
基金Supported by the Ministerio De Ciencia Y Technologia(NoSB2004-oobo)
文摘A variety of gold（Ⅲ） adducts having a-ligated oxygen-donor ligands have been prepared from [Au（ppy）Cl2]（ppy.phenylpyridine）（1） either by partial or total replacement of the chloride ions. The new species comprise hydroxo-[Au（ppy）（OH）Cl]（2）, and [Au（ppy）（OH）2]（3）, oxo-[Au2（ppy）2（μ-O）2]（4）, acetate-[Au（ppy）（O2CMe2）] （5）, and alkoxo complexes-[Au（ppy）（OR）Cl]（6, 7） and [Au（ppy）（OR）2]（8--10）（R=Me, 6 and 8; Et, 7 and 9; Pr, 10）. The dihydroxo and the oxo complexes can be interconverted by refluxing the former in anhydrous THF and the latter in water. The hydroxides 2 and 3 and the acetato complex 5 undergo σ-ligand metathesis in ROH solution（R=Me, Et or Pr） to give the corresponding alkoxides.
基金the Deanship of Scientific Research at Princess Nourah bint Abdulrahman University,through the Research Funding Program(#RFP-1440-3)。
文摘The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for future drug design.New Au(Ⅲ)nanosized complexes of cefotaxime(ceph-3)and cefepime(ceph-4)ligands as a 3rd and 4th of cephalosporin generation drugs were synthesized.Gold(Ⅲ)complexes were discussed based on the elemental,molar conductance,thermal and magnetic moment measurements as well as spectral(FTIR,1HNMR,UV-Vis,and XRD)techniques.FT-IR spectra revealed that the ceph-3 and ceph-4 ligands reacted as a bidentate ligands through carboxylate oxygen andβ-lactam oxygen groups.The analytical analysis confirm that the molar ratio is 1∶1(Au 3+/ceph)with general formula[Au(L)(Cl)2]where L=ceph-3 or ceph-4.The structures of Au(Ⅲ)complexes were presence as a square planar geometry.X-ray diffraction patterns referred to a crystalline nature for all synthesized complexes.TEM analyses confirmed that the synthetic gold(Ⅲ)complexes have a nanosized particles.In vitro antimicrobial activities of Au(Ⅲ)complexes were evaluated towards two types of bacteria(G+&G-).The antitumor activities of gold(Ⅲ)complexes are appraised against breast(MCF-7)and colorectal adenocarcinoma(Caco-2)cell lines,which means that the two complexes may consider promising anticancer drugs.
基金Supported by the Natural Science Foundation of Hebei Province(No.2 0 2 140 ) and Hebei Education Departm ent(No.2 0 0 112 1)
文摘The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).
文摘Thermodynamic properties and electrochemical behaviors of gold and its associated elements, such as silver, copper, nickel and iron, in various complex agent solutions were studied. Within CS（NH2）2, S2O2-3 and SCN- systems, alkaline thiourea is the optimal nontoxic lixiviating agent substituting cyanide from the viewpoint of thermodynamics. The electrochemical study indicates that the anodic dissolution current densities of gold are 2.616, （1.805,） 1.267, 1.088, 0.556, and 0.145 mA·cm-2 respectively in the solutions of cyanide, alkaline thiourea containing Na2SiO3, SCN-, acidic thiourea, alkaline thiourea and thiosulfate at the potential of 0.500 V. Comparing various lixiviating agents, the alkaline thiourea solution containing Na2SiO3 is of prominent selectivity in leaching gold, in the potential range from 0.500 to 0.600 V, which is most efficient for leaching gold selectively instead of cyanide. The effect on leaching gold is similar to that in the cyanide system.
文摘A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.
基金the China Scholarship Council for a personal financial grant(no.201606200045)supported by the European Research Council via a Starting GrantDutch Research Council(NWO)for a VICI grant to S.Bonnet.
文摘Gold complexes have emerged as promising anticancer metallodrugs due to their efficient thioredoxin reductase(TrxR)inhibition,which disturbs the redox balance of cancer cells.However,in this model,the role of the ligand(s)coordinated to gold is often overlooked.In this work,we present a series of tetrapyridyl Au(Ⅲ)complexes that exhibit thiol-induced release of a Au(Ⅰ)ion and a tetrapyridyl ligand.The formation of a free Au(Ⅰ)center is responsible for the expected TrxR inhibition.Additionally,the released ligand,which was visible in cells due to its intense blue fluorescence,showed excellent binding properties to the hERG potassium channel.Moreover,these ligands ended up in the lysosomes,resulting in significant lysosome damage.Altogether,the Au(Ⅲ)complexes presented in this work showed broad-spectrum anticancer properties,both in hypoxic 2D monolayers and 3D tumor spheroids.We suggest that the interaction of the released Au(Ⅰ)center and the tetrapyridyl ligand with two different protein targets may combine into prodrugs that overcome hypoxia-induced drug deactivation.
基金supported by the Construct Program of the Key Discipline in Hunan Province
文摘A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.
文摘Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.
文摘The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓
基金Ph.D. Programme at the Department of Chemistry, University of Kerala, India
文摘A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].
