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.     

铕(Ⅲ)-锌(Ⅱ)双核配合物的合成和表征

Two new Eu(Ⅲ)-Zn(Ⅱ) binuclear complexes Zn(Salen)EuL₃ have been synthesized, where Salen=Shiff base of bissalicylaldehyde with ethlenediamine and L=acetylacetone (for complex Ⅰ) or trifluoroacetylacetone (for compelx Ⅱ). Analytical experimetal such as IR, UV and elemental analysis suggest the possible component and structure, the fluorescence spectrum of the complex Ⅱ suggests the M^*→M fluorescence mechanism.     

不同配体对钌多吡啶配合物与DNA的作用和荧光性质的影响

Two polypyridyl ligands DCHIP (2-hydro-3，5-dichlorophenyl-imidazo[4，5-f][1，10] phenanthroline)，MDHIP(2，4-dihydrophenyl-imidazo[4，5-f][1，10]phenanthroline) and their ruthenium(Ⅱ) complexes [Ru(phen)₂MDHIP]²⁺ and [Ru(phen)₂DCHIP]²⁺ were prepared. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode， but [Ru(phen)₂DCHIP]²⁺ exhibited stronger binding affinity for DNA than [Ru(phen)₂MDHIP]²⁺ due to the different planarities and steric effects of ligands. On the other hand， after binding to DNA， the fluorescence intensity of [Ru(phen)₂MDHIP]²⁺ decreased， while the fluorescence intensity of [Ru(phen)₂ DCHIP]²⁺ increased.     

具2,3-二氯-5,6-二腈基对苯醌自由基阴离子(DDQ-·)的Fe(Ⅱ)三元配合物的合成及性质

In this paper the ternary complexes of Fe(Ⅱ),DDQ^-·,and L[L=o-phenanthroline (phen),2, 2'-bip yridine (bipy),2, 2'-bipyridine-N,N'-dioxide(bipyO₂),salicyloylhydrazine(shH),and Cl^-,respectively]were synthesized The chemical compositions of the com-plexes w ere deteim fined by elem ental analysis, and their structures and p roperties w ere researched by 1R,UV-Vis, ⁵⁶FeM ssbauer spectra, molar conductivities, solid conductivities and DTA.     

锌(Ⅱ)-氨基酸水杨醛席夫碱-α-氨基酸三元配合物的稳定性

The stability constants of binary complexes of Zn(Ⅱ)-α-amino acid and ternary complexes of Zn(Ⅱ)-N-Salicylideneaminio acid (ligand A)-α-amino acid(ligand B) at (25±0.1)℃ and in the presence of 0.1 mol·L^-1 KNO₃ have been determined by pH method. The α-amino acid(Aa) used were Glycine(Gly), L-Serine(Ser), L-Leucine(Leu), L-Proline(Pro) and L-Phenylalanine(Phe). It was found that the linear free energy relationship (LFER) exists nicely between the following parameter pairs logβ₁₀₂ and pK^B₂, logβ₁₁₁ and pK^B₂, and logβ₁₁₁ and pK^A₂. The ΔlgK was used to characterize the stability of ternary complexes related to the stability of parent binary complexes. The hydrophobic interaction between ligands in the ternary complexes was studied.     

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.     

对三氟甲基苯甲酸和2，2′-联吡啶双核铽配合物的合成、晶体结构及发光性质

A new dinuclear complex [Tb₂(BA)₆(2,2′-bipy)₂] (BA=4-(trifluoromethyl)benzoic acid, 2,2′-bipy=2,2′-bipyridine) has been synthesized. The complex was characterized by X-ray single-crystal structure analysis. The complex is a dimer with an inversion center. In the complex, two Tb3+ ions are linked by four carboxylate groups of BA ligands in bridging-bidentate coordination mode. Each Tb³⁺ ion is eight-coordinated with two nitrogen atoms from one 2,2′-bipy molecule, four oxygen atoms from four bridging-bidentate BA ligands and two oxygen atoms from one chelating-bidentate BA ligand. Intermolecular hydrogen bonds are formed in the crystal. The complex exhibits strong green fluorescence under ultraviolet light and the fluorescence spectrum consists of four lines peaking at 489, 545, 584 and 620 nm, which are corresponding to the ⁵D₄→⁷F_j (j=6～3) transitions of Tb³⁺ ion, respectively. CCDC: 727763.     

新型超分子复合发光材料——联吡啶氮氧化物铕配合物-蒙脱土的室温固相插层组装及发光性能

Eu(Ⅲ) complexes with bipyO₂ ligand were intercalated into the interlayer spacing of montmorillonite (MMT) by solid-solid ion exchanging and coordination reaction of bipyO₂ with the Eu³⁺ ion existing in the interlayer spacing of Eu-MMT at room temperature, respectively. The obtained luminescent supramolecular composite materials, [Eu(bipyO₂)₄Cl₂]⁺-MMT and [Eu(bipyO₂)₄]³⁺-MMT were characterized by elemental analysis, XRD and FTIR spectroscopy. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalation assembly materials have regular layered structures and good luminescent properties. They emit characteristic red emissions of Eu³⁺ strongly under ultraviolet light excitation. The relative luminescence intensities of the unit mass of Eu³⁺ of intercalation assemblies are much better than that of the corresponding pure Eu³⁺ complex possibly due to the rigid layered structures of the materials and the supramolecular interaction between the host layers and the guest complex ions.     

meso-四(对烷氧基苯基)卟啉配合物的合成、表征和液晶性研究

The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe³⁺, Mn³⁺, Pb²⁺, Co²⁺, Cu²⁺, Zn²⁺. Among them there were seven new compounds. All these compounds were identified through ¹H NMR, MS, IR, UV and Element analysis. The correlation between the structure of compounds and their ¹H NMR, MS, IR, UV spectra was discussed and their specific spectra were explained. We found nine metalloporphyrins exhibited liquid crystal behaviour through DSC and polarized-light microscope. They had one to three mesophases and certain phase transition temperature, ΔH and temperature range of L.C(ΔT).     

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.     

Luminescent properties of Tb3+ and Gd3+ ions doped aluminosilicate oxyfluoride glasses

Tb³⁺ and Gd³⁺ ions doped lithium–barium–aluminosilicate oxyfluoride glasses have been prepared. The transmission, emission and excitation spectra were measured. It has been found that those Tb³⁺-doped lithium–barium–aluminosilicate oxyfluoride glasses exhibit good UV-excited luminescence. The luminescence intensity of Tb³⁺ ion increases for those (Tb³⁺, Gd³⁺)-codoped glasses. Energy transfer process from Gd³⁺ ion to Tb³⁺ ion is indicated.     

Formation of complexes of Rubisco-Rubisco activase from La3+, Ce3+ treatment spinach

The complex of Rubisco and Rubisco activase from LaCl₃ ^™, CeCl₃ ^™ treated spinachin vivo is induced. SDS-PAGE result shows that the purified proteins from LaCl₃ ^™, CeCl₃ ^™ treated spinach have not only large and small subunits (55 kD, 14.4 kD) of Rubisco, but also two large subunits of 45 kD and 41 kD near the large subunits of Rubisco. Native-PAGE shows that the purified proteins from LaCl₃ ^™, CeCl₃ ^™ treated spinach have not only a band of Rubisco (560 kD), but also a band of about 1100 kD, about twice distant from Rubisco, which might be a complex of Rubisco and Rubisco activase. The purified enzyme activities from LaCl₃ ^™, CeCl₃ ^™ treated spinach are 1.8 and 2.8 times that of the control, the intensities of absorption and fluorescence are significantly higher than that of the purified Rubisco from the control, and the total sulfhydryl groups and available sulfhydryl groups are 36–39 ™SH per mol enzyme, 14–25 ™SH per mol enzyme more than those of the purified Rubisco from the control, respectively. The CD spectra show that the secondary structure of the purified enzyme from LaCl₃ ^™, CeCl₃ ^™ treated spinach is very different from the control. The enzyme activities from LaCl₃ ^™, CeCl₃ ^™ treated spinachin vivo are 1.5 and 1.9 times those of the control.     

Er~(3+)-Yb~(3+)双掺Li_2O-ZnO-SiO_2系透明玻璃陶瓷的制备及表征

采用熔融-晶化技术合成了Er3+-Yb3+掺杂的Li2O-ZnO-SiO2系(LZS)透明玻璃陶瓷。利用DTA,XRD,SEM,UV-Vis-NIR等对样品进行了表征,并分析了影响玻璃陶瓷析晶的因素。结果表明,LZS系玻璃具有良好的结晶性能,其最佳热处理温度为700℃,最佳热处理时间为50min,其主晶相为石英和Li8Zn10Si7O28。该玻璃陶瓷在可见光区的透过率可达85%。经SEM分析,粒子直径为30~40nm。荧光光谱显示,玻璃陶瓷的发射光谱较之基质玻璃有了极大的提高,而且在1530nm附近获得一较强发射峰。     

A new lawsone azo-dye for optical sensing of Fe3+ and Cu2+ and their DFT study

A new lawsone-based azo-dye 2-hydroxy-3-((pyridin-2-ylmethyl)diazenyl)naphthalene-1,4-dione (1) was synthesized and applied for sensing of metal ions. Receptor 1 showed selective fluorescent and colorimetric response for the detection of Cu²⁺ and Fe³⁺ over other tested metal ions. The fluorescence intensity of 1 was significantly quenched allowing detection of Fe³⁺ and Cu²⁺ down to 0.61 and 6.06 μM, respectively. The binding has been established by fluorescence spectroscopic method. Receptor 1 provided a 1?:?1 binding scaffold for recognition of Fe³⁺ and Cu²⁺ ions with the association constant of 3.33 × 10⁶ and 3.33 × 10⁵ M^?1, respectively. The B3LYP/6-31G/LANL2DZ method was employed for the optimization of 1 and 1·Fe³⁺ and 1·Cu²⁺.     

Novel naphthalene-based fluorescent chemosensors for Cu2+ and Fe3+ in aqueous media

Three novel compounds bearing 2,7-dihydroxylnaphthalene capable of detecting Cu²⁺ or Fe³⁺ have been synthesised based on photoinduced electron transfer. The ability of these compounds for complex transition metal ions has been studied, and complex stoichiometry for Cu²⁺ and Fe³⁺ complex has been determined in the Tris–HCl (0.01 M DMSO/H₂O (v/v) 1:1, buffer, pH 7.4) solution system by fluorescence titration experiments. These chemosensors form a 1:1 complex with Cu²⁺ or Fe³⁺ and show a fluorescent quenching with a binding constant of (4.46 ± 0.29) × 10³ and (8.04 ± 0.26) × 10⁴, respectively.     

Perimedine-linked rhodamine dye in visual sensing of Al3+, Fe3+ and Fe2+ ions in aqueous organic medium under different experimental conditions

ABSTRACT

Perimedine labelled rhodamine dye 1 has been designed and synthesised. Metal ion binding studies of 1 have been performed in CH₃CN/H₂O (3:1, v/v, 10 mM Tris-HCl buffer, pH = 6.90). Compound 1 senses multiple metal ions such as Al³⁺, Fe³⁺ and Fe²⁺ by exhibiting turn on fluorescence and colour change (colourless to pink) under different experimental conditions. Concentration variation distinguishes Al³⁺ from Fe³⁺ ion. At low concentration (c = 1 x 10^?4 M), only Al³⁺ ion can exhibit turn on fluorescence with sharp colour change. Sensing of Fe²⁺ ion through turn on fluorescence and colour change has been possible via in situ oxidation by following Fenton’s reaction.     

Er3+-Yb3+掺杂SiO2-SrO-NaF玻璃陶瓷的制备及表征

采用熔融晶化法制备了主晶相为SrF₂的Er³⁺-Yb³⁺共掺透明氟氧化物玻璃陶瓷,利用DSC、XRD、SEM、UV-Vis-NIR和荧光光谱对样品的结构、形貌、发光性能进行了测试与表征。研究表明：该体系玻璃最佳热处理温度为620℃,最佳热处理时间为2 h,并讨论了Yb³⁺不同掺杂浓度对Er³⁺-Yb³⁺共掺玻璃陶瓷样品上转换发光性能的影响,确定Er³⁺-Yb³⁺最佳掺杂浓度比为1：7,同时观察到了明亮的绿光（522,540 nm）和较弱的红光（656 nm）,对Er³⁺和Yb³⁺之间的能量传递过程进行了讨论。     

Study on the synthesis of novel fluorescent macrocyclic sensors and their sensitive properties for Cu2+ and Fe3+ in aqueous solution

In this work, we synthesised and characterised three novel fluorescence macrocyclic sensors containing optically active dansyl groups. The studies for the interaction of the synthesised compounds with various mental ions (Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Ca²⁺, Ba²⁺, Pb²⁺, Zn²⁺, Co²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Cr³⁺, Al³⁺, Fe³⁺) were performed by fluorescence titration, Job’s plot, ESI-MS and DFT calculations. The results showed that the sensors 1a–1c displayed selective recognition for Cu²⁺ and Fe³⁺ ions and formed stoichiometry 1:1 complex through PET mechanism in DMSO/H₂O solution (1:1, v/v, pH 7.4 of HEPES). The binding constant (K) and detection limit were calculated.     

Sm3+与Nd3+离子在LaOX系列基质中的配位场微扰能级及其光谱解析

合成了LaOX:Sm³⁺和LaOX:Nd³⁺磷光体(X^-=Cl^-,Br^-),测定了它们在空温和液氮温度下的荧光光谱;基于双层点电荷配位场模型,对其荧光光谱进行了理论归属,并讨论了基质对希土离子晶场效应的影响等问题.