This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
Iron deficiency anemia affects approximately 1.62 billion people worldwide,yet traditional iron supplements present bioavailability limitations and gastrointestinal side effects.This randomized,double-blind clinical t...Iron deficiency anemia affects approximately 1.62 billion people worldwide,yet traditional iron supplements present bioavailability limitations and gastrointestinal side effects.This randomized,double-blind clinical trial investigated a novel Auricularia auricula polysaccharide-iron complex(AAPIC)compared with heme iron and ferrous glycinate in 180 iron-deficient adults receiving 30 mg elemental iron daily for 12 weeks.AAPIC achieved comparable hemoglobin improvements(from 98.3±8.7 to 126.5±9.2 g/L)to heme iron(from 97.8±9.1 to 128.3±8.6 g/L)and was significantly superior to ferrous glycinate(from 98.6±8.9 to 119.7±10.3 g/L;p<0.001).Iron absorption efficiency showed AAPIC at 23.7±4.2%,heme iron at 25.1±3.8%,and ferrous glycinate at 18.4±5.1%.Toxicological assessments revealed no hepatotoxicity,nephrotoxicity,or mutagenicity.Gastrointestinal adverse events occurred in 8.3%of AAPIC recipients versus 15.0%with ferrous glycinate and 10.0%with heme iron.The polysaccharide component facilitates iron transport through enhanced intestinal uptake mechanisms.AAPIC represents a promising,well-tolerated alternative with clinical efficacy comparable to established iron formulations.展开更多
Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been s...Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied.Here,the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied.It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances.The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light,respectively.The concentration of phenolic hydroxyl groups increased from 10.0~57.5 mmol/gC to 6.6~65.2 mmol/gC,and the concentration of carboxyl groups increased from49.7~97.5 mmol/gC to 62.1~113.3 mmol/gC.Then the impacts of DBC on pyrite dissolution andmicroalgae growth were also investigated.The complexing Fe^(3+)was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution.Due to complexing between iron ion and DBC,the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions.Fe-DBC complexations in solution significantly promoted microalga growth,which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis.The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.展开更多
The cerium iron complex oxides oxygen carrier was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. Th...The cerium iron complex oxides oxygen carrier was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. The reduced oxygen carder could be re-oxidized by air and its initial state could be restored. The characterizations of the oxygen carders were studied using XRD, O2-TPD, and H2-TPR. The results showed that the bulk lattice oxygen of CeO2-Fe2O3 was found to be suitable for the partial oxidation of methane to synthesis gas. There were two kinds of oxygen species on the oxygen carrier： the stronger oxygen species that was responsible for the complete oxidation of methane, and the weaker oxygen species （bulk lattice oxygen） that was responsible for the selective oxidation of methane to CO and H2 at a higher temperature. Then, the lost bulk lattice oxygen could be selectively supplemented by air re-oxidation at an appropriate reaction condition. CeFeO3 appeared on the oxygen carrier after 10 successive redox cycles, however, it was not bad for the selectivity of CO and H2.展开更多
Angelica sinensis polysaccharide（ASP） was extracted from Angelica sinensis by boiling water. An Angelica sinensis polysaccharide-iron complex（APC） was prepared under the alkaline condition by adding a ferric chlor...Angelica sinensis polysaccharide（ASP） was extracted from Angelica sinensis by boiling water. An Angelica sinensis polysaccharide-iron complex（APC） was prepared under the alkaline condition by adding a ferric chloride solution to the ASP solution. Then some identifiable properties of the complex were studied. The content of iron（ Ⅲ ） in the complex was determined with iodometry. The thermal property, the microscopic structure, the spectral characteristics, and N, C, H contents of the complex were examined by a variety of techniques including DSC, TEM, IR, NMR, and elemental analysis. The content of iron（ Ⅲ ） in the complex ranges from 10% to 40%. The DSC result shows that the melting point of the complex is about 450 ℃. The TEM result shows that the complex has an iron（ Ⅲ ） core（β-FeOOH core） linked by hydroxy and oxy bridges, with the polysaccharide chains attached to the surface of the core. The IR and NMR results also show that there is a β-FeOOH core in the complex. The elemental analysis shows that the contents of N, C, H in the complex are, respectively, lower than those of N, C, H in ASP. All our studies indicate that the APC consists of a β-FeOOH core surrounded by ASP.展开更多
Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum sugge...Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.展开更多
The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, ...The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.展开更多
A new dinuclear iron（Ill） complex has been synthesized and structurally charac- terized by X-ray crystallography： [Fem2（L）（C6HsCOO）（SO4）（CH3OH）2]·CH3CN＇CH3OH （1, H3L = N,N＇-bis（salicylidene）q,3-di...A new dinuclear iron（Ill） complex has been synthesized and structurally charac- terized by X-ray crystallography： [Fem2（L）（C6HsCOO）（SO4）（CH3OH）2]·CH3CN＇CH3OH （1, H3L = N,N＇-bis（salicylidene）q,3-diamino-2-propanol）. Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400（8）, b = 22.9705（2）, c = 12.5712（9）A, V= 3303.5（4）A3, Z= 4, F（000） = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.展开更多
Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of ea...Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).展开更多
The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster wit...The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.展开更多
A new thiolate-bridged diiron complex with two mono-coordinated azido ligands, [Cp＊Fe（kt-SMe）N3]2 （Cp^＊ = η^5-C5Me5）, was synthesized from [Cp＊Fe（η-SMe）MeCNMPF6]2 and NaN3 in a bi-solvent system of acetone ...A new thiolate-bridged diiron complex with two mono-coordinated azido ligands, [Cp＊Fe（kt-SMe）N3]2 （Cp^＊ = η^5-C5Me5）, was synthesized from [Cp＊Fe（η-SMe）MeCNMPF6]2 and NaN3 in a bi-solvent system of acetone and methanol. X-ray crystal structural analysis shows that the compound belongs to the orthorhombic Fdd2 space group, with a = 14.3771（15）, b = 71.424（8）, c = 9.7010（10）A, V = 9961.7（18） A3, C22H36Fe2N6S2, Mr = 560.39, Dc = 1.495 g/cm^3, F（000） = 4704,μ（MoKa） = 1.355 mm-I and Z = 16. The compound consists ofa di（u-thiolate）diiron unit {Cp＊Fe（p-SMe）}2, in which each iron is coordinated by a terminal azido ligand. Magnetic characterizations show spin canting behavior for the title compound.展开更多
The methylene-selective oxidation of simple alkanes catalyzed by a nonheme iron(Ⅲ)-monoamidate complex using H_(2)O_(2)as the terminal oxidant is reported.Mechanistic studies suggest that iron(V)-oxo species is the a...The methylene-selective oxidation of simple alkanes catalyzed by a nonheme iron(Ⅲ)-monoamidate complex using H_(2)O_(2)as the terminal oxidant is reported.Mechanistic studies suggest that iron(V)-oxo species is the active intermediate,undergoing hydrogen atom abstraction(HAA)as the rate-determining step to initiate C-H bond activation.展开更多
High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been ...High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been developed in the difunctionalization of alkenes in the presence of radical initiator.However,the details of the reaction mechanism are still unclear,especially the transformations of the photocatalyst and the iron catalyst during the catalytic turnover.Herein,we expanded the photo-driven non-heme iron complex catalyzed thiocyanation of styrene substrate.This protocol exhibited broad substrate scope and high efficiency.Detailed mechanistic studies using various spectroscopies,such as UV-vis,mass spectrometry,transient absorption spectroscopy and X-ray absorption spectroscopy,revealed the transformations of photocatalyst[Ir^(Ⅲ)(ppy)_(3)]and group transfer catalyst[Fe^(Ⅱ)(bpmen)]^(2+).Real-time spectroscopies combined with mechanistic experiments demonstrated that[Ir^(Ⅳ)(ppy)_(3)]^(+)and[Fe^(Ⅲ)(bpmen)]^(3+)were the key intermediates involved in the reaction cycle.展开更多
A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometr...A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.展开更多
Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3&...Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3·Se2C2B 10H 10（3）. The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral.展开更多
The discovery of highly active 2,6-bis（imino）pyridyl iron and cobalt complexes provided a milestone of latetransition metal catalysts for ethylene oligomerization and polymerization with being currently investigated...The discovery of highly active 2,6-bis（imino）pyridyl iron and cobalt complexes provided a milestone of latetransition metal catalysts for ethylene oligomerization and polymerization with being currently investigated for the scale-up process. The crucial problems are remaining in the catalytic systems： the catalytic systems targeting ethylene polymerization produce more oligomers at elevated reaction temperatures, however, there is a recognizable amount of high-molecularweight polyethylene remained in the modified catalytic system for the oligomerization process. Beyond the modification of bis（imino）pyridyl metal complexes, several alternative proeatalysts＇ models have been developed in our group. This review highlighted the achievements in exploring new iron and cobalt complexes with tridentate NNN ligands as procatalysts for ethylene oligomerization and polymerization.展开更多
A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8....A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.展开更多
A series of biopolymer based complex were manufactured by coordinating iron ions to the abundant amino-and sulfur-containing groups in the modified wool and used as heterogeneous Fenton-like photocatalyst for 4-chloro...A series of biopolymer based complex were manufactured by coordinating iron ions to the abundant amino-and sulfur-containing groups in the modified wool and used as heterogeneous Fenton-like photocatalyst for 4-chlorophenol (4-CP) degradation in the presence of H2O2. Hydroxylamine hydrochloride (NH2OH center dot HCl) or acrylic acid was employed to modify the natural wool to strengthen the interaction with iron and to reinforce the structural stability. The NH2OH center dot HCl modified wool based complex showed the best catalytic performance for 4-CP degradation. The strong coordination between iron and great number of hydroxamic acid in this modified complex leads to the least iron leaching during the tests. HO center dot species was confirmed to be the dominant reactive oxidant in the decontamination process. The approach presented in this study can provide a new approach for developing novel bioployermer-based photocatalysts for efficient degradation of toxic organic pollutants such as 4-CP. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based cata...Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based catalysts demonstrated excellent catalytic activity and enantioselectivity in the asymmetric epoxidation of electron-deficient olefins using H_(2)O_(2) as the terminal oxidant.展开更多
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
文摘Iron deficiency anemia affects approximately 1.62 billion people worldwide,yet traditional iron supplements present bioavailability limitations and gastrointestinal side effects.This randomized,double-blind clinical trial investigated a novel Auricularia auricula polysaccharide-iron complex(AAPIC)compared with heme iron and ferrous glycinate in 180 iron-deficient adults receiving 30 mg elemental iron daily for 12 weeks.AAPIC achieved comparable hemoglobin improvements(from 98.3±8.7 to 126.5±9.2 g/L)to heme iron(from 97.8±9.1 to 128.3±8.6 g/L)and was significantly superior to ferrous glycinate(from 98.6±8.9 to 119.7±10.3 g/L;p<0.001).Iron absorption efficiency showed AAPIC at 23.7±4.2%,heme iron at 25.1±3.8%,and ferrous glycinate at 18.4±5.1%.Toxicological assessments revealed no hepatotoxicity,nephrotoxicity,or mutagenicity.Gastrointestinal adverse events occurred in 8.3%of AAPIC recipients versus 15.0%with ferrous glycinate and 10.0%with heme iron.The polysaccharide component facilitates iron transport through enhanced intestinal uptake mechanisms.AAPIC represents a promising,well-tolerated alternative with clinical efficacy comparable to established iron formulations.
基金supported by the National Natural Science Foundation of China(Nos.42207450,42067056,and 21866017)the Yunnan Fundamental Research Projects(No.202101BE070001-013)the Foundation for Distinguished Young Talents of Yunnan Province(No.202101AV070006).
文摘Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied.Here,the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied.It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances.The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light,respectively.The concentration of phenolic hydroxyl groups increased from 10.0~57.5 mmol/gC to 6.6~65.2 mmol/gC,and the concentration of carboxyl groups increased from49.7~97.5 mmol/gC to 62.1~113.3 mmol/gC.Then the impacts of DBC on pyrite dissolution andmicroalgae growth were also investigated.The complexing Fe^(3+)was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution.Due to complexing between iron ion and DBC,the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions.Fe-DBC complexations in solution significantly promoted microalga growth,which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis.The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.
基金the National Natural Science Foundation of China (50574046)National Natural Science Foundation of Major Research Projects (90610035)+1 种基金Natural Science Foundation of Yunnan Province (2004E0058Q)High School Doctoral Subject Special Science and Research Foundation of Ministry of Education (20040674005)
文摘The cerium iron complex oxides oxygen carrier was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. The reduced oxygen carder could be re-oxidized by air and its initial state could be restored. The characterizations of the oxygen carders were studied using XRD, O2-TPD, and H2-TPR. The results showed that the bulk lattice oxygen of CeO2-Fe2O3 was found to be suitable for the partial oxidation of methane to synthesis gas. There were two kinds of oxygen species on the oxygen carrier： the stronger oxygen species that was responsible for the complete oxidation of methane, and the weaker oxygen species （bulk lattice oxygen） that was responsible for the selective oxidation of methane to CO and H2 at a higher temperature. Then, the lost bulk lattice oxygen could be selectively supplemented by air re-oxidation at an appropriate reaction condition. CeFeO3 appeared on the oxygen carrier after 10 successive redox cycles, however, it was not bad for the selectivity of CO and H2.
文摘Angelica sinensis polysaccharide（ASP） was extracted from Angelica sinensis by boiling water. An Angelica sinensis polysaccharide-iron complex（APC） was prepared under the alkaline condition by adding a ferric chloride solution to the ASP solution. Then some identifiable properties of the complex were studied. The content of iron（ Ⅲ ） in the complex was determined with iodometry. The thermal property, the microscopic structure, the spectral characteristics, and N, C, H contents of the complex were examined by a variety of techniques including DSC, TEM, IR, NMR, and elemental analysis. The content of iron（ Ⅲ ） in the complex ranges from 10% to 40%. The DSC result shows that the melting point of the complex is about 450 ℃. The TEM result shows that the complex has an iron（ Ⅲ ） core（β-FeOOH core） linked by hydroxy and oxy bridges, with the polysaccharide chains attached to the surface of the core. The IR and NMR results also show that there is a β-FeOOH core in the complex. The elemental analysis shows that the contents of N, C, H in the complex are, respectively, lower than those of N, C, H in ASP. All our studies indicate that the APC consists of a β-FeOOH core surrounded by ASP.
文摘Styrene-acrylic acid copolymer (SAAC)-supported iron complex (SAAC·Fe)was characterized and the effect of the characteristic parameters on the catalytic activity of the complex was investigated. IR spectrum suggested that the complex SAAC·Fe possesses a structure of(C)and the Fe-O bond is higher in covalency.The complex SAAC·Fe with the structure of(C)shoved a higher catalytic activity in butadiene polymerization. When Fe/-COOH molar ratio in SAAC·Fe was about 0.2 the complex gave optimum catalytic activity. The catalytic activity of SAAC·Fe with the higher content of long sequence of acrylic acid units was low. When the content of the short sequence of acrylic acid units was predominant and at the same time the content of the short sequence was approximately equal to that of the long sequence for stryrene, the activity of the complex was high.
基金Financially Supported by the National Natural Science Foundation of China (29974029, 29925101) and Special Funds for Major State Basic Research Projects of China (G1999064800)
文摘The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.
基金Supported by the Natural Science Foundation of Mongolian Autonomous Region,China(No.2014MS0215)
文摘A new dinuclear iron（Ill） complex has been synthesized and structurally charac- terized by X-ray crystallography： [Fem2（L）（C6HsCOO）（SO4）（CH3OH）2]·CH3CN＇CH3OH （1, H3L = N,N＇-bis（salicylidene）q,3-diamino-2-propanol）. Complex 1 belongs to orthorhombic space group Pna21 with a= 11.4400（8）, b = 22.9705（2）, c = 12.5712（9）A, V= 3303.5（4）A3, Z= 4, F（000） = 1576, Dc= 1.531 g·cm-3, Mr= 761.36,μ = 1.007 mm-1, S = 1.014, the final R= 0.0505 and wR= 0.1018. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters ofJ= 19.7 cm-1, g = 1.89 and R2 = 0.9999.
基金Supported by the National Natural Science Foundation of China(No.2 0 1730 0 6 )
文摘Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).
基金supported by the National Natural Science Foundation of China(Nos.21266019,21062011 and 21462029)Inner Mongolia Autonomous Region Higher Scientific Research Project(NJZY14060)
文摘The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
基金supported by NNSFC (21231003, 20972023, 21076037)
文摘A new thiolate-bridged diiron complex with two mono-coordinated azido ligands, [Cp＊Fe（kt-SMe）N3]2 （Cp^＊ = η^5-C5Me5）, was synthesized from [Cp＊Fe（η-SMe）MeCNMPF6]2 and NaN3 in a bi-solvent system of acetone and methanol. X-ray crystal structural analysis shows that the compound belongs to the orthorhombic Fdd2 space group, with a = 14.3771（15）, b = 71.424（8）, c = 9.7010（10）A, V = 9961.7（18） A3, C22H36Fe2N6S2, Mr = 560.39, Dc = 1.495 g/cm^3, F（000） = 4704,μ（MoKa） = 1.355 mm-I and Z = 16. The compound consists ofa di（u-thiolate）diiron unit {Cp＊Fe（p-SMe）}2, in which each iron is coordinated by a terminal azido ligand. Magnetic characterizations show spin canting behavior for the title compound.
文摘The methylene-selective oxidation of simple alkanes catalyzed by a nonheme iron(Ⅲ)-monoamidate complex using H_(2)O_(2)as the terminal oxidant is reported.Mechanistic studies suggest that iron(V)-oxo species is the active intermediate,undergoing hydrogen atom abstraction(HAA)as the rate-determining step to initiate C-H bond activation.
基金supported by the National Natural Science Foundation of China(22171216)the National Key R&D Program of China(2021YFA1500100).
文摘High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been developed in the difunctionalization of alkenes in the presence of radical initiator.However,the details of the reaction mechanism are still unclear,especially the transformations of the photocatalyst and the iron catalyst during the catalytic turnover.Herein,we expanded the photo-driven non-heme iron complex catalyzed thiocyanation of styrene substrate.This protocol exhibited broad substrate scope and high efficiency.Detailed mechanistic studies using various spectroscopies,such as UV-vis,mass spectrometry,transient absorption spectroscopy and X-ray absorption spectroscopy,revealed the transformations of photocatalyst[Ir^(Ⅲ)(ppy)_(3)]and group transfer catalyst[Fe^(Ⅱ)(bpmen)]^(2+).Real-time spectroscopies combined with mechanistic experiments demonstrated that[Ir^(Ⅳ)(ppy)_(3)]^(+)and[Fe^(Ⅲ)(bpmen)]^(3+)were the key intermediates involved in the reaction cycle.
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101).
文摘A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.
基金Supported by the National Natural Science Foundation of China( No.2 99740 2 9,2 992 5 10 1) and Special Funds forMajor State Basic Research Projects of China( G19990 64 80 0)
文摘Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3·Se2C2B 10H 10（3）. The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral.
文摘The discovery of highly active 2,6-bis（imino）pyridyl iron and cobalt complexes provided a milestone of latetransition metal catalysts for ethylene oligomerization and polymerization with being currently investigated for the scale-up process. The crucial problems are remaining in the catalytic systems： the catalytic systems targeting ethylene polymerization produce more oligomers at elevated reaction temperatures, however, there is a recognizable amount of high-molecularweight polyethylene remained in the modified catalytic system for the oligomerization process. Beyond the modification of bis（imino）pyridyl metal complexes, several alternative proeatalysts＇ models have been developed in our group. This review highlighted the achievements in exploring new iron and cobalt complexes with tridentate NNN ligands as procatalysts for ethylene oligomerization and polymerization.
基金The project was supported by NNSFC (20001007 20131020) and NSF of the Chinese Academy of Sciences (KJCX2-H3) and Fujian Province (2000F006)
文摘A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.
基金National Natural Science Foundation of China (grant nos.51268001,21303141) for support of this work
文摘A series of biopolymer based complex were manufactured by coordinating iron ions to the abundant amino-and sulfur-containing groups in the modified wool and used as heterogeneous Fenton-like photocatalyst for 4-chlorophenol (4-CP) degradation in the presence of H2O2. Hydroxylamine hydrochloride (NH2OH center dot HCl) or acrylic acid was employed to modify the natural wool to strengthen the interaction with iron and to reinforce the structural stability. The NH2OH center dot HCl modified wool based complex showed the best catalytic performance for 4-CP degradation. The strong coordination between iron and great number of hydroxamic acid in this modified complex leads to the least iron leaching during the tests. HO center dot species was confirmed to be the dominant reactive oxidant in the decontamination process. The approach presented in this study can provide a new approach for developing novel bioployermer-based photocatalysts for efficient degradation of toxic organic pollutants such as 4-CP. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
文摘Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based catalysts demonstrated excellent catalytic activity and enantioselectivity in the asymmetric epoxidation of electron-deficient olefins using H_(2)O_(2) as the terminal oxidant.
