Investigation on the coordinate structures of the rare earth metal complexes with edta and cydta ligands

0　IntroductionThegreatattentionhasbeenpaidtorareearthorradioactiverareearthmetalcomplexesfortheirvariousbiologicactivi ties[1 3] .Forexamples,theradioactiverareearthmetal1 53SmⅢ com plexeswerewidelyusedfortumourtherapyofbrain ,liver,lung ,heartandbonetissues[4 5] ;forrareearthmetalEuⅢandTbⅢemitinguniquefluorescence ,theircompoundswereappliedfordiagnosesofvariousdiseases[6 ,7] ;forrareearthmetalGdⅢcontainingthemosthigh spinsingleelectrons,itscomplexeswereusuallyusedforcontrastagentsofmag…     

Experimental and kinetic study on ignition delay times of methane/hydrogen/oxygen/nitrogen mixtures by shock tube

Ignition delay times of methane/hydrogen/oxygen/nitrogen mixtures with hydrogen amount-of-substance fractions ranging from 0–20% were measured in a shock tube facility.The ambient temperature varied from 1422 to 1877 K and the pressure was maintained at 0.4 MPa behind the reflected shock wave.The experiments were conducted at an equivalence ratio of 2.0.The fuel mixtures were diluted with nitrogen gas so that the nitrogen amount-of-substance fraction was 95%.The experimental ignition delay time of the CH4/H2 mixture decreased as the hydrogen amount-of-substance fraction increased.The enhancement of ignition by hydrogen addition was weak when the ambient temperature was >1750 K,and strong when the temperature was <1725 K.The ignition delay time of 20% H2/80% CH4 was only one-third that of 100% CH4 at 1500 K.A modified model based on GRI-Mech 3.0 was proposed and used to calculate the ignition delay times of test mixtures.The calculated results agreed with the experimental ignition delay times.Normalized sensitivity analysis showed that HO·+H2 →H·+H2O was the main reaction for the formation of the H· at 1400 K.As the hydrogen amount-of-substance fraction increased,chain branching was enhanced through the reaction H·+O2→O·+HO·,and this reduced the ignition delay time.At 1800 K,the methyl radical (H3C·) became the key species that influenced the ignition of the CH4/H2/O2/N2 mixtures,and sensitivity coefficients of the chain termination reaction 2H3C·(+M)→C2H6(+M),and chain propagation reaction HO2+H3C·→HO·+CH3O decreased,which reduced the influence of hydrogen addition on the ignition of the CH4/H2 mixtures.     

冷凝液硫含量对SUS444铁素体不锈钢腐蚀行为的影响

利用冷凝液浸蚀-高温氧化循环腐蚀法模拟汽车排气系统内部服役环境,借助失重分析、腐蚀形貌观察及腐蚀产物分析,研究了SUS444不锈钢在不同硫含量的冷凝液中的腐蚀行为。结果表明,随着腐蚀循环次数的增加,不锈钢表面不断沉积的FeSO_4·7H_2O、Fe(NH_4)(SO_4)_2及Fe_4(SO_4)_5(OH)_2·18H_2O等硫酸盐物质加速了不锈钢的腐蚀进程,其点蚀深度及腐蚀速率均随冷凝液中硫含量的升高而增加。     

Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

Structure and magnetism of carboxylate/EO-azido-mixed-ligands bridged CuII systems

Using two structurally related benzoates bearing different H-bond acceptors as co-ligands, three new azido-Cu^Ⅱ compounds, [Cu（L^1）（N3）（H2O）]n（1）, [Cu（L^1）（N3）（MeOH）]n （2）, and [CuL^2HL^2（N3）3（H2O）]n（3） （HL^1 = 4-nitrobenzoic acid; HL^2= 2-phenyl-4-quinolinecarboxylic acid）, have been synthesized and structurally characterized. 1 is a carboxylate/EO-azido bridged copper chain, forming 3D structure by H-bonds, and 2 has a similar chain structure as 1 but forming a 2D structure by H-bonds, while 3 is a 3D supramolecular network with ternary center H-bonds. Magnetic study indicates that domain ferromagnetic coupling interactions were found to exist in complexes 1 and 3.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Syntheses,structure and photoluminescent properties of lanthanide oxalatosulfocarboxylate coordination polymers

Hydrothermal reactions of oxalic acid(H2ox) and 2-sulfobenzoic acid(H2L) with lanthanide oxide or hydroxide yielded five lanthanide oxalatosulfocarboxylates.They have a general formula [Ln2L2(ox)(H2O)6]n[Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5)].Their structures were characterized by single crystal X-ray diffraction,powder X-ray diffraction(PXRD),infrared(IR) spectroscopy,elemental analysis(EA),and thermogravimetric analysis(TGA).1-5 are isostructural coordination polymers and feature one-dimensional(1D) chains,which are extended into 3D supramolecular frameworks through inter-chain hydrogen bonds between coordinated H2O donors and oxygen acceptors from carboxylate,sulfonate and oxalate groups.In addition,the solid-state photoluminescence properties of the Nd(2),Eu(3) and Tb(5) derivatives have been measured at room temperature.The Eu and Tb-containing coordination polymers(CPs) exhibit intense red and green luminescence emissions,respectively,with lifetimes in the order of millisecond.     

Synthesis, crystal structure and properties of binuclear manganese complex [(bipy)2Mn2(μ-O)(μ-Ac)2(H2O)2](ClO4)2

Binuclear manganese complex [(bipy)₂Mn₂(μ-O)(μ-Ac)₂(H₂O)₂](ClO₄)₂ was synthesized by the reaction of MnAc₃ · 2H₂O with 2,2′-bipyridine in the HAc-NaAc buffer (pH = 4.0). X-ray diffraction result for the single crystal shows that the crystal is monoclinic, space group C₂/C, with a = 3.408 2(7),b = 0.864 4(2),c = 2.174 9(4) nm, β= 105.2∘, V=6.186(2) nm³, Z= 8. There are two very strong peaks of UV-Vis spectrum in the range of 400–600 nm, which are similar to those of Mn catalase and Mn ribonuleotide reductase extracted from organisms. Cyclic voltammogram shows that the complex in CH₃CN undergoes quasi-reversible one-electron reduction and oxidation at E_1/2=1.15V.     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

Efficient and selective recovery of Ni,Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)₉S₈ and FeNi₃, Cu₅FeS₄, and (Fe,Ni)₉S₈ and Fe₃O₄ (in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH₄)₂S₂O₈/NH₃·H₂O solution system was studied. The effects of (NH₄)₂S₂O₈ and NH₃·H₂O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte.     

葡聚糖产生菌(Leuoconostoc mesenteroides)发酵培养基优化初步研究

采用单一因素确定法研究分离自明阳糖厂的一株肠膜明串珠菌菌株摇瓶发酵生产葡聚糖的适宜培养基 ,结果得到适宜培养基的组分为 :蔗糖 1 0 %、酵母膏 0 .4%、磷酸氢二铵0 .6%、磷酸二氢钾 0 .1 %、硫酸镁 0 .1 %、Mn Cl2 · 4H2 O0 .0 0 0 3%、Zn SO4· 7H2 O0 .0 0 0 5%、Fe SO4· 7H2 O0 .0 0 5%、Ca Cl2 · 2 H2 O0 .0 0 2 %。     

Crystal structure and magnetism of the binuclear Gd(III) complex Gd2(C12H8N2)2(C6H5COO)6

In the medium of H₂O, C₂H₅OH and HAC, the reaction of Gd(NO₃)₃·6H₂O with C₆H₅COONa and C₁₂H₈N₂ produced a novel binuclear Gd(III) complex in formula [Gd₂(C₁₂H₈N₂)₂ (C₆H₅COO)₆]. Crystallographic data: crystal system, triclinic; space group, P1; unit cell dimensions, a=1.191 9(2) nm,b =1.244 2(2) nm,c = 1.080 4(2) nm, α = 93.57(3)°, β= 113.33(3)°, γ= 105.06(3)°, Z=l. The finalR =0.037 6. The magnetic measurement of the crystal powder in the temperature region of 1.5–300 K shows that this complex possesses antiferromagnetic property with fitting magnetic parametersJ = −0.471 andg =1.975.     

Electroless copper-phosphorus coatings with the addition of silicon carbide (SiC) particles

Cu-P-silicon carbide (SiC) composite coatings were deposited by means of electroless plating. The effects of pH values, temperature, and different concentrations of sodium hypophosphite (NaH₂PO₂·H₂O), nickel sulfate (NiSO₄·6H₂O), sodium citrate (C₆H₅Na₃O₇·2H₂O) and SiC on the deposition rate and coating compositions were evaluated, and the bath formulation for Cu-P-SiC composite coatings was optimised. The coating compositions were determined using energy-dispersive X-ray analysis (EDX). The corresponding optimal operating parameters for depositing Cu-P-SiC are as follows: pH 9; temperature, 90℃; NaH₂PO₂·H₂O concentration, 125 g/L; NiSO₄·6H₂O concentration, 3.125 g/L; SiC concentration, 5 g/L; and C₆H₅Na₃O₇·2H₂O concentration, 50 g/L. The surface morphology of the coatings analysed by scanning electron microscopy (SEM) shows that Cu particles are uniformly distributed. The hardness and wear resistance of Cu-P composite coatings are improved with the addition of SiC particles and increase with the increase of SiC content.     

Composition design of superhigh strength maraging stainless steels using a cluster model

The composition characteristics of maraging stainless steels were studied in the present work investigation using a cluster-plus-glue-atom model. The least solubility limit of high-temperature austenite to form martensite in basic Fe–Ni–Cr corresponds to the cluster formula [NiFe12]Cr3,where NiFe12is a cuboctahedron centered by Ni and surrounded by 12 Fe atoms in FCC structure and Cr serves as glue atoms. A cluster formula [NiFe12](Cr2Ni) with surplus Ni was then determined to ensure the second phase(Ni3M) precipitation,based on which new multicomponent alloys [(Ni,Cu)16Fe192](Cr32(Ni,Mo,Ti,Nb,Al,V)16) were designed. These alloys were prepared by copper mould suction casting method,then solid-solution treated at 1273 K for 1 h followed by water-quenching,and finally aged at 783 K for 3 h. The experimental results showed that the multi-element alloying results in Ni3M precipitation on the martensite,which enhances the strengths of alloys sharply after ageing treatment. Among them,the aged [(Cu4Ni12)Fe192](Cr32(Ni8.5Mo2Ti2Nb0.5Al1V1)) alloy(Fe74.91Ni8.82Cr11.62Mo1.34Ti0.67Nb0.32Al0.19V0.36Cu1.78wt%) has higher tensile strengths with YS?1456 MPa and UTS?1494 MPa. It also exhibits good corrosion-resistance in 3.5 wt% NaCl solution.     

微波辐射下苯氧乙酸锌、甘氨酸锌的固相合成及表征

研究了乙酸锌与苯氧乙酸,甘氨酸在微波辐射及这曙条件下的固－固相配位化学反应,通过固相反应一步合成了苯氧乙酸锌和甘氨酸锌。经电导率,ＩＲ,ＵＶ及元素分析表征了产物。     

Magnetic properties of heteropolyoxometalates

The progress of the study on the magnetic properties of heteropolyoxometalates during the late decade is reviewed. Some anions of heteropolyoxometalates containing magnetic atoms, such as [M4(H2O)4(PW9O34)2]10- and[M4(H2O)4(P2W15O56)2]16-[M = Co(Ⅱ), Zn( Ⅱ ), Cu( Ⅱ ), Mn(Ⅱ ), Ni(Ⅱ)], and [GaW9O37M3(H2O)3]n-[M = Fe(Ⅲ), Cu(Ⅱ), Co(Ⅱ)] showed ferromagnetic and antiferromagnetic properties. The combination of heteropoly anions and organic π-donor of TTF+ (te-trathiofulvalene cation) results in a variety of magnetic properties. Furthermore, there is an interaction between the inorganic and organic components. The electrocrystallization technique can prepare the organic-inorganic salts of this kind, which will become the new member of molecular magnetic materials. Heteropoly blue is a kind of the mixed-valence complexes and its reduction electrons can be delocalized over anionic framework. The further study on the magnetic properties of heteropolyoxometalates will provide important information for the design of molecular materials.     

Micro-arc oxidization fabrication and ethanol sensing performance of Fe-doped TiO<Subscript>2</Subscript> thin films

In-situ pure TiO₂ and Fe-doped TiO₂ thin films were synthesized on Ti plates via the micro-arc oxidation (MAO) technique. The as-fabricated anatase TiO₂ thin film-based conductometric sensors were employed to measure the gas sensitivity to ethanol. The results showed that Fe ions could be easily introduced into the MAO-TiO₂ thin films by adding precursor K₄(FeCN)₆·3H₂O into the Na₃PO₄ electrolyte. The amount of doped Fe ions increased almost linearly with the concentration of K₄(FeCN)₆·3H₂O increasing, eventually affecting the ethanol sensing performances of TiO₂ thin films. It was found that the enhanced sensor signals obtained had an optimal concentration of Fe dopant (1.28at%), by which the maximal gas sensor signal to 1000 ppm ethanol was estimated to be 7.91 at 275°C. The response time was generally reduced by doped Fe ions, which could be ascribed to the increase of oxygen vacancies caused by Fe³⁺ substituting for Ti⁴⁺.     

Synthesis,characterization and photoluminescence of aluminum <Emphasis Type="Italic">N</Emphasis>-aryloxo functionalized <Emphasis Type="Italic">β</Emphasis>-ketoiminate complexes

The synthesis, characterization and luminescent properties of aluminum complexes containing a dianionic N-aryloxo functionalized β-ketoiminate ligand are presented. 4-(2-Hydroxy-5-R-phenyl)imino-2-pentanone (R = Me, L¹H₂; R = tert-butyl, L²H₂) ligands reacted with AlEt₃ in tetrahydrofuran to give the aluminum complexes (L¹AlEt)₂ (1) and (L²AlEt)₂ (2) in reasonable isolated yields. X-ray diffraction revealed that complexes 1 and 2 have solvent-free centrosymmetric dimeric structures, and each aluminum center has distorted trigonal bipyramidal geometry. At room temperature, complexes 1 and 2 exhibit blue photoluminescence in acetonitrile with maximum emission wavelengths of 419 and 413 nm, respectively.     

A novel hydrothermal method for zinc extraction and separation from zinc ferrite and electric arc furnace dust

A novel hydrothermal process was developed to extract zinc from pure zinc ferrite (ZnFe₂O₄) nanopowder and zinc-containing electric arc furnace (EAF) dust using hexahydrated ferric chloride (FeCl₃·6H₂O) as a decomposing agent. The effects of solid FeCl₃·6H₂O to ZnFe₂O₄ ratio by mass (R_F/Z), hydrothermal reaction temperature, and time on zinc extraction were systematically investigated. In the results, when the hydrothermal reaction is conducted at 150℃ for 2 h with R_F/Z of 15:20, the efficiency of zinc extraction from ZnFe₂O₄ reaches 97.2%, and the concentration of ferric ions (Fe3+) in the leaching solution is nearly zero, indicating a high selectivity for zinc. In addition, the zinc extraction efficiency from the EAF dust reaches 94.5% in the case of the hydrothermal reaction performed at 200℃ for 10 h with the solid FeCl₃·6H₂O to EAF dust ratio by mass (R_{F/EAF dust}) of 15:10. Zinc and iron separation is achieved by adjusting the pH value of the leaching solution according to the different precipitation pH values of metal hydroxides.     

Phase behavior and properties of salt-free cationic/anionic surfactant mixtures of oleic acid and stearic acid

Cationic base surfactant, tetradecyltrimethylammonium hydroxide （TTAOH）, can be obtained through anion exchange from tetradecyltrimethylammonium bromide （TTABr）. Salt-free cationic and anionic （catanionic） surfactant mixtures were studied by mixing TTAOH with oleic acid （OA） or stearic acid （SA） in water. The phase behavior of TTAOH/OA/H2O is compared with that of TTAOH/SA/H2O. It was found that the phase behavior of TTAOH/OA/H2O and TTAOH/SA/H2O system differs from each other due to the existence of the unsaturated double carbon bond （C=C） in OA. At fixed total surfactant concentration （25 mg/mL） of TTAOH/ONH2O system at 25℃, one can observe an isotropic L1 phase, and a L1/Lα two-phase region with increasing OA content. The volume of top turbid Lα phase increases while the bottom phase changes gradually from transparently clear to a bit turbid until a single Lα-phase is reached. Finally at high OA concentration, excess OA is separated from the bulk aqueous solutions. TTAOH/SA/H2O system usually forms white precipitating at 25℃ due to the high chain melting temperature of SA. When heated to 60℃, however, the state of samples changes. At fixed total surfactant concentration of 25 mg/mL, an isotropic Lα phase and a milk-white or bluish Lα-phase are observed with increasing SA concentration. Transparent thin layers which are strongly birefringent form at the tops of some samples within the Lα-phase region. Finally, at high SA concentration, excess SA is separated from the bulk aqueous solutions. In addition to phase behavior study, we also measured the conductivity of TTAOH/OA/H2O system at 25℃ and TTAOH/SA/H2O system at 60℃, respectively. Surface tension and rheological measurements were also performed on typical samples.