手性配体立体选择性萃取分离扁桃酸对映体

Based on chiral ligand exchange, the distribution behavior of mandelic acid enantiomers in the two-phase system containing copper ion(Ⅱ)(Cu²⁺) and N-n-dedecane-L-hydroxyproline (L), was studied. At different pH, the partition of Cu²⁺ in the two-phase system containing N-n-dedecane-L-hydroxyproline, was investigated. The formation constant of binary cpmplex(Li₂Cu) was obtained by regression. The influence of pH, concentrations of Cu²⁺ and chiral ligand, and solvents on partition coefficients(K) and separation factor(α), was discussed. The experimental results show that Li forms more stable ternary complex with D-mandelic acid than with L- mandelic acid. There is a large influence of pH on K and α. At low pH values (<3.5), formation of binary complexes is thermodynamically unfavourable. K and α are best when pH values are above 3.5 and the molar ratio of chiral ligand to Cu²⁺ is 2∶1. At the same time, solvents influence K and α very much.     

2-十四烷基-DTPA及其钆(Ⅲ)螯合物的合成与表征(英)

Synthesis and characterization of the ligand, [2-tetradecyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, H₅L] and its Gd(Ⅲ) chelate are described. Protonation constants for H₅L (lgK_i^H = 10.80, 8.40, 4.30, 2.80, 2.15) and the stability constant for GdL^2- (lgK_GdL^2-= 22.75) were determined by potentiometric titration and are similar with the related values of DTPA and Gd-DTPA respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after introduction of a linear chain tetradecyl group at the terminal acetic acid residue of DTPA.     

N，N，N′，N′-四丁基丙二酰胺从硝酸盐介质中萃取铈(Ⅲ)

Study on the extraction and separation of rare earth with new extractants is important in the rare earth chemistry and nuclear reprocessing. In this work， the extraction of Ce(Ⅲ) with N，N，N′，N′-tetrabutylmalonamide (TBMA) in toluene from nitrate media has been investigated. The effect of the concentration of nitric acid， TBMA and salt-ing-out agent (LiNO₃) and also the temperature on the distribution ratios was examined. The stoichiometries of the extracted complexes were determined to be Ce(NO₃)₃·3TBMA and Ce(NO₃)₃·4TBMA， respectively. The ap-parent extraction constants and the enthalpy of the extraction were calculated based on the extraction data， which are logK_ex1=3.97， logK_ex2=4.75 and Δ_rH_m^?=-31.25kJ·mol^-1， respectively. The IR spectra of the loaded organic phase supported the suggested extraction mechanism.     

α-十四烷基-DOTA及其钆(Ⅲ)螯合物的合成与表征(英)

Synthesis and characterization of the ligand, [10-(α-tetradecylcarboxymethyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid, H₄L] and its Gd(Ⅲ) chelate are described. Protonation constants for H₄L(lgK_i^H = 10.62, 9.50, 4.74, 4.12) and the stability constant for GdL^-(lgK_GdL^-= 24.60) were determined by potentiometric titrations. The results obtained show that the basicity of the ligand is not significantly altered and the ligand still maintains the strong chelating properties of the parent DOTA after introduction of a linear chain tetradecyl group at the acetic side chain of DOTA.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

稀土与β-二酮及2-（2-吡啶）苯并咪唑三元配合物的研究

As useful fluorescent reagent, rare earth complexes with β-diketones have been　extensively studied. Four new rare earth (La, Eu) ternary complexes with　β-diketones, (benzoylacetone (Hbza), 2-thenoyltrifluoroacetone, (HTTA)) and organic base (2-(2-pyridyl) benzimidazole, (Hpbi)) have been synthesized and characterized by elemental analysis, IR, NMR. The general formulae of these complexes are ［Ln(bza)₃(Hpbi)］ and［Ln(TTA)₃(Hpbi)］. The effects of coordinated base on UV, especially on fluorescent properties of the complexes were discussed. The results showed that the dehydro-Hpbi, pbi^{－, strongly enhances the fluorescence of the complexes.}     

4-(3-吲哚基)-3-丁烯-2-酮苯甲酰腙Schiff碱过渡金属配合物的合成、表征及生物活性研究

A Schiff base ligand 4-[indol-3-yl]-but-3-en-2-one benzoyl hydrazone (HL), and its four transition metal complexes (ML₂，M=Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) and Co(Ⅱ)) have been prepared and characterized by means of elemental analysis, EI-MS, molar conductivity, IR, UV-Vis and ¹H NMR. The results showed that HL as a bidentate ligand coordinated with transition metal ions to form four-coordination complexes. The antibacterial activity was studied by using the filter scraps diffusion method, and the results indicated that the ligand and the complexes had a low bacteriostatic activity against S. Aureu, P. Aeruginosa and E. Coli. The low in vitro antitumor activity of the title complexes was also observed by using MTT method against KB, A2780, Bel7402 and HELF.     

微波辐射固相法合成缩二脲铜配合物

The copper(Ⅱ) complexes of biuret have been synthesized by solid phase reaction with microwave irradiation. The compositions and structures of the complexes are characterized by elemental analysis, molar conductance, in-frared spectra, electronic spectra, magnetic susceptibility, thermogravimetric and differential thermal analysis, X-ray powder diffraction. The two complexes have the compositions of [Cu(bi)₂]Cl₂(A) and [Cu(bi)₂](NO₃)₂(B)(bi=NH₂CONHCONH₂) and the molecular formulae of CuC₄H₁₀O₄N₆Cl₂ and CuC₄H₁₀O₁₀N₈, respectively. The molar conductance data show that the complexes are 1∶2 electrolyte. Infrared spectra of the complexes show oxygen atoms have been coordinated with divalent copper ion. The thermal decomposition processes of the complexes show that the final residues are all cupper oxide. The results of indexes to the X-ray powder diffraction data indicate that the crystal structure of the complexes belong to monoclinic system, the lattice parameters are: a=0.6976nm,b=1.1546 nm,c=2.1689nm,β=96.80°,V=1.7346nm³ for A; and a=0.7096nm,b=1.1359 nm,c=2.1002 nm,β=97.05°,V=1.6800nm³ for B, respectively.     

配合物稳定性与酸碱强度之间的直线自由能关系——ⅪⅤ.N-(取代苯基)亚氨基二乙酸与铜(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)钴(Ⅱ)二元配合物的稳定性研究

The dissociation constants of N-(para-substituted phenyl) iminodiacetic acid (p-RPhID A, R= Cl, H, CH₃, CH₃O) and N-(ortho-substituted phenyl) iminodiacetic acid (o-RPhlDA) and the formation constants of binary complex compounds of Cu(Ⅱ)-o-RPhIDA, Cu(Ⅱ)-p-RPhIDA, Co(Ⅱ)-p-RPhIDA, Ni(Ⅱ)-p-RPhIDA and Zn(Ⅱ)-p-RPhIDA were determined by pH method in the presence 0.1mol·dm^-3KNO₃ at 25℃ . It has been found that linear free energy relationships not only exist between stability of these binary complex compounds and base strength of ligand, but also exist between logβ and σ'(=pK₂-pK₂).The deviation of Cu(Ⅱ)-o-CH₃PhIDA from linearity may be ascribed to steric effect of methyl group at ortho position.     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

Magnetic, spectral, and thermal behaviour of 2-chloro-4-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Some physicochemical properties of 2-chloro-4-nitrobenzoates of Co(II), Ni(II), and Cu(II) were studied. The complexes were obtained as mono-and dihydrates with a metal ion—ligand mole ratio of 1: 2. All complexes are polycrystalline compounds. Their colours depend on the kind of central ion: pink for Co(II) complex, green for Ni(II), and blue for Cu(II) complexes. Their thermal decomposition was studied only in the range of 293 K–523 K because it was found that on heating in air above 523 K 2-chloro-4-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step. During dehydration process no transformation of the nitro group to nitrito one took place. Their solubilities in water at 293 K are of the orders of 10⁻³-10⁻² mol dm⁻³. The magnetic moment values of 2-chloro-4-nitrobenzoates determined in the range of 76 K–303 K change from 3.48μ_B to 3.82μ_B for Co(II) complex, from 2.24μ_B to 2.83μ_B for Ni(II) 2-chloro-4-nitrobenzoate, and from 0.31μ_B to 1.41μ_B for Cu(II) complex. 2-Chloro-4-nitrobenzoates of Co(II) and Ni(II) follow the Curie—Weiss law, but the complex of Cu(II) forms dimer.     

Thermal and Spectral Behaviour of 5-chloro-2-methoxybenzoates of Heavy Lanthanides and Yttrium

5-Chloro-2-methoxybenzoates of heavy lanthanides and yttrium were obtained as di- or tetrahydrates with a metal to ligand ratio of 1:3 and general formula: Ln(C₈H₆ClO₃)₃⋅nH₂O, where n=2 for Ln=Tb, Dy, Y and n=4 for Ln=Ho, Er, Tm, Yb, Lu. The complexes were characterized by elemental analysis, IR and FIR spectra, thermogravimetric studies, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical, bidentate, chelating ligand. All complexes are polycrystalline compounds. Their thermal stabilities were determined in air and in nitrogen atmospheres. When heated they dehydrate to form anhydrous salts which next in air are decomposed to the oxides of the respective metals while in nitrogen to the mixtures of carbon and oxides or carbon and oxychlorides of respective metals. The complexes are more stable in air than in nitrogen. The solubilities of yttrium and heavy lanthanide 5-chloro-2-methoxybenzoates in water at 293 K are of the order of 10^–3 mol dm^–3 The magnetic moments of the complexes were determined over the range 77–298 K. They obey the Curie–Weiss law. The values of μ_eff calculated for all compounds are close to those obtained for Ln³⁺ by Hund and Van Vleck. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature. This revised version was published online in August 2006 with corrections to the Cover Date.     

非离子型L-赖氨酸长链酯-双EDTA酰胺钆配合物的合成与弛豫效能

Four novel ester-amino ligands were synthesized by bis-acylation of octadecanyl, hexadecanyl, tetradecanyl and dedecanyl L-lysinate with ethylenediaminetetraacetic acid mono-anhydride (EDTA-MA), respectively. The corresponding neutral dimeric Gd(Ⅲ) complexes were gained by reacting these ligands with GdCl₃·6H₂O. All ligands and complexes were characterized by FTIR, ¹H NMR and elemental analysis. The longitunal relaxation time (T₁) was measured, and their stability were investigated by competition with Ca²⁺ and EDTA. The results indicate that the relaxivity of these netral binuclear Gd(Ⅲ) complexes are higher than that of Gd-DTPA.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum（Ⅱ） Complexes

The stability constants of some ternary mixed-ligand complexes, Pt (Phen)(CA) , where Phen-1,10-phenanthroline and CA^-=carboxylate, were determined by means of potentiometric pH titration in aqueous solutions (I=0. 1mol/L, KNO3; 25℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands (PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen) (PCA)^- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

L-苏糖酸锰的制备及标准生成焓

The pink powder of manganese L-threonate was obtained by extracting with alcohol the concentrated solution derived from the reaction between L-threonic acid solution prepared by double decomposition reaction of calcium L-threonate with oxalic acid and superfluous manganese oxide at 80℃ for certain time. The composition of the new compound was determined by chemical and elemental analyses and its formula fits Mn(C₄H₇O₅)₂·H₂O, the IR spectra indicated that Mn²⁺ in the compound coordinates to oxygen atom of the carboxyl group, while the proton of the carboxyl group is dissociated, it was assumed that the coordination number of Mn²⁺ was 4. The results of TG-DTG showed that the compound have fairish stability, the intermediate and final product of the thermal de-composition of the compound are Mn(C₄H₇O₅)₂ and MnO₂, respectively. The constant volume combustion energy of the compound, Δ_cE, were determined by a precise rotating-bomb calorimeter at 298.15K, it was (-3384.30±1.21)kJ·mol^-1, its standard enthalpy of Combustion,Δ_cH_m^?,and standard enthalpy of formation,Δ_fH_m^? , were calculated. They are (-3383.07±1.21)kJ·mol^-1 and (-2 571.68±1.63)kJ·mol^-1, respectively.     

噻吩甲酰基吡唑啉酮缩氨基酸稀土配合物的合成、表征及生物活性

A new amino-acid Schiff base, 1-phenyl-3-methyl-4-(2-thenoyl) pyrazolone-5-β-alanine (HL) and its ten rare earth complexes have been synthesized. On the basis of elemental analysis and molar conductance, the general formula of the complexes, [REL₂NO₃]·nH₂O (RE=La, Nd, Eu, Tb, Y, n=2; RE= Pr, Sm, n=1; RE= Dy, Er, Yb, n=3), is given. They were characterized by IR, UV-visible, ¹H NMR, ¹³C NMR and fluorescence. The results show that the rare earth ions exhibit coordination of eight in the complexes.The antibacterial experiments indicate that they have high antibacterial activities against S. Aureus, B. Subtillis, E. Coli, E. Carotovora and C. Flaccumfaciens.     

配合物稳定性和配体酸碱强度之间的直线自由能关系──铜(Ⅱ)、锌(Ⅱ)-芬布芬-α-氨基酸三元配合物体系

在25±0.1℃,I=0.1mol·dm^-3KNO₃条件下,80%(v/v)DMSO-H₂O混合溶剂中,应用pH法测定了甘氨酸,L一缬氨酸,L-异亮氨酸,L-脯氨酸,L-丝氨酸,DL-苯丙氨酸等六种α-氨基酸(缩写为α-AA,记为B配体)的酸离解常数,铜(Ⅱ)-α-氨基酸。锌(Ⅱ)-α-氨基酸二元配合物的稳定常数及铜(Ⅱ)-芬布芬-α-氨基酸(芬布芬缩写为Fen,记为A配体)和锌(Ⅱ)-芬布芬-α-氨基酸三元配合物的稳定常数。实验发现,在下面三对参数之间,即logβ₁₀₂与pK₂^B,lOgβ₁₁₁;与pK₂^B及10gβ₁₁₁与logβ₁₀₂,均存在良好的直线自由能关系。用△logK_M和△logβ₁₁₁两个参量描述了三元配合物相对于母体二元配合物的稳定性。讨论了溶剂的性质,配合物分子内配体之间的疏水作用,芳环之间的堆积作用对配合物稳定性的影响。     

钐与1-苯基-2，3-二甲基-4-酰代吡唑酮-5的三元配合物的合成与表征

Four new Sm(Ⅲ) ternary complexes with 1-phenyl-2,3-dimethyl-4-acethlpyrazolone-5 (HPDMAP) or 1-phenyl-2,3-dimethyl-4-trichloroacethlpyrazolone-5 (HPDMCP) as the ligand: Sm(PDMAP)₃·bipy (A₁), Sm(PDMAP)₃·phen (A₂), Sm(PDMCP)₃·bipy(B₁) and Sm(PDMCP)₃·phen (B₂) (Where bipy=2,2′-dipyridyl, phen=1,10-phenanthroline.) were synthesized and identified by elemental analysis. They were characterized by UV and FT-IR spectra analysis. Their luminescence from the solid state were studied. The results show that the fluorescence intensities of B₁ and B₂ are stronger than those of A₁ and A₂, but they all have the same order magnitude. As far as A₁ and A₂, B₁ and B₂ are concerned, both bipy and phen have affect on the fluorescence intensities of the complexes.     

钾的N-酰化牛磺酸配合物的合成、表征及其晶体结构

The title complex(K(C₉H₁₃NO₅S₂)(H2O)) was synthesized by the reaction of p-tolysulfonyl chloride, taurine and potassium hydrate in water-methanol-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 336.44. The crystal structure of the title complex belongs to orthorhombic space group Pbca and cell parameters: a=0.853 31(12) nm, b=0.820 42(12) nm, c=3.989 4(6) nm. V=2.792 8(7) nm³, Z=8, D_c=1.600 g·cm^-3, μ=0.699 mm^-1, F(000)=1 400. The compound is an one-dimension chain complex of infinite length which are connected with hydrogen bond and bridging coordination water. The difference and same of the complexes were discussed. CCDC: 244938.     

金属离子与卟啉的嵌入反应动力学研究——邻苯二甲酸缓冲溶液中溴化间-四(N-乙酸甲酯基-3-吡啶基)卟啉与Cu(Ⅱ)的配位反应

Kinetics of the coordination reaction of tetrakis(N-carbomethoxymethyl-3-pyridyl) porphyrin(abbr. H₂T_β-N-ACMSPyP) with Cu(Ⅱ) ion has been studied in o-phthalic acid buffer system in an ionic strength of 0.5mol·dm^-3(KCI) at 35.0±0.1℃.The reaction is catalyzed by o-phthalic ion. The effect of concentration of the cata-lyst, metal ion and pH value of solution was discussed. The kinetics equation of the reaction were obtained as d[CuP⁴⁺]/dt=16.15{(1.0+3.35×10⁵[PT^2-]²)/1.0+1.57×10^-4[H⁺]²}[Cu²⁺][P]_T. The mechanism of the reaction was proposed. The deformation of the ring of porphyrins is the general condition in the reaction.