Synthesis,characterization, and fluorescence properties of lanthanide complexes with poly(styrene‐co‐methacrylic acid)

A series of new complexes of poly(styrene‐co‐methacrylic acid) with Ln(III) (Ln = La, Eu, Tb) were synthesized and well characterized by means of elemental analysis, FTIR, differential scanning calorimetric (DSC) analysis, TG‐DTA analysis, X‐ray diffraction (XRD), and fluorescence determination. The elemental analysis and FTIR studies showed that a large part of carboxylic groups on the side chain of the copolymer are coordinated with Ln(III) ions. The TG‐DTA and DSC analysis results indicated that the complexes have good thermal stability. XRD experiments showed that copolymers and the complexes are amorphous. Among these complexes, Eu(III) complexes and Tb(III) complexes exhibit characteristic fluorescence with comparatively high brightness and good monochromaticity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

重稀土2-噻吩甲酸配合物的合成及Tb3+的发光

合成了4种稀土与2-噻吩甲酸(L)配合物。通过元素分析、稀土配合滴定及摩尔电导确定其化学组成为REL3.2H2O(RE=Gd,Tb,Dy,Er),并对配合物进行了红外光谱、荧光激发和发射光谱测定。红外光谱测定表明,配体通过羧基以螯合双齿的方式与稀土离子(Ⅲ)配位成键。荧光光谱数据表明,铽配合物具有良好的荧光性能。     

Study on macromolecular lanthanide complexes (V): Synthesis,characterization, and fluorescence properties of lanthanide complexes with the copolymers of styrene and acrylic acid

In this study, the luminescent macromolecular lanthanide complexes Ln‐PSt/AA (Ln = Eu and Tb; St = styrene; AA = acrylic acid) have been synthesized, and an extensive characterization has been carried out by means of elemental analysis, FTIR, thermal analysis, and fluorescence determination. The results showed that the carboxylic groups on the chain of the polymers acted as bidentate ligands coordinated to lanthanide ions; and the coordination degree of ? COO^?/Ln³⁺ in the macromolecular complexes was closely dependent on both the pH value of the solution and the molar ratio of St to AA in the polymeric ligands. Thermal analysis manifested that these Ln‐PSt/AA (Ln = Eu and Tb) complexes had high thermal stability and solvent resistance, and these macromolecular complexes were highly crosslinked. The fluorescence determination indicated that Ln‐PSt/AA complexes could emit characteristic fluorescence with comparatively high brightness and good monochromaticity, and the fluorescence intensity changed with increasing lanthanide ions content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

糠醛缩邻氨基苯甲酸Schiff碱稀土配合物的合成与表征

合成了糠醛缩邻氨基苯甲酸Schiff碱及其4种稀土配合物,并通过元素分析、IR、UV、1H NMR和热失重分析对其组成和结构进行表征,结果表明,配体是以四齿的形式参与配位,配位数为8,配合物的组成为Re(L)2.2.5H2O(Re=Eu、Sm、La、Y)。     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

手性联萘酚稀土配合物的合成及荧光性能研究

在无水无氧条件下,以氯化钐、氯化钆和R-联萘酚为原料室温合成了手性联萘酚稀土配合物{[(THF)2Na]3[Sm(R-BINOLate)3]}(1)和{[(THF)2Na]3[Gd(R-BINOLate)3]}(2),对所合成的配合物进行了荧光性能研究。研究表明,在λex=392 nm的最佳激发波长监控下,配合物(1)和(2)固体状态下都能发出粉红色荧光,配合物(1)的发射波长为662 nm、强度355 a.u.;配合物(2)的发射波长为652 nm、强度78 a.u.,均为联萘酚微扰的中心金属离子Sm3+,Gd3+的5D0→7F3特征吸收峰。     

Synthesis and fluorescence properties of novel 1,10‐phenanthroline‐functionalized polyaryletherketone and its rare earth complexes

1,10‐Phenanthroline‐functionalized polyaryletherketone (PPEK) was synthesized by the amidation reaction of 5‐amino‐1,10‐phenanthroline with polyaryletherketone containing pendant acyl chloride groups. Subsequently, a series of novel rare earth coordination polymers (with rare earths Eu³⁺, Tb³⁺, Sm³⁺ and Dy³⁺) were prepared, using PPEK as macromolecular ligand and the small 1,10‐phenanthroline (Phen) molecule as synergistic ligand. Their structures were characterized using Fourier transform infrared spectroscopy, elemental analysis and X‐ray diffraction, which confirmed that both PPEK and Phen participated in the coordination reaction with the rare earth ions, and that the rare earth ions could disperse homogeneously in the polymer matrix. The rare earth coordination polymers were soluble in polar solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide and N‐methylpyrrolidone, and could be easily cast into transparent tough thin films. Fluorescence measurements indicated that all the coordination polymers exhibited the intense characteristic fluorescence of the corresponding rare earth ions under ultraviolet excitation, showing their application potential in optical display devices. Copyright © 2010 Society of Chemical Industry     

稀土配合物及其共聚物的合成与性能研究

以丙烯酸(HAA)、甲基丙烯酸(HMA)及1,10-邻菲罗啉(Phen)为配体与氧化铕(Eu2O3)反应得到二元配合物Eu(AA)3、Eu(MA)3和三元配合物Eu(AA)3Phen、Eu(MA)3Phen。将生成的配合物与HMA和甲基丙烯酸甲酯(MMA)共聚,得到一系列三元共聚物。通过元素分析、红外光谱、荧光光谱和热分析对配合物进行了分析与表征,发现配合物具有良好的荧光强度和热稳定性。三元配合物的荧光强度相对于二元配合物有显著提高。共聚物可发射Eu3+的特征荧光,荧光强度随配合物含量的增加而增加,且未发生浓度猝灭现象。三元配合物在反应单体MMA和HMA中的溶解度低于二元配合物,从而使在最大溶解度下二元配合物与反应单体生成共聚物的荧光强度高于相应的三元配合物与反应单体生成的共聚物。     

二茂铁丙烯酰羟胺稀土金属配合物的合成与表征

合成了二茂铁丙烯酰羟胺FcCH=CHCONHOH(HL)，并以此为配体与氯化稀土（RECl3)反应，合成了14种稀土金属配合物，通过元素分析，红外光 谱，核磁共振氢谱及紫外光谱对化合物进行了表征。     

新型酰基吡唑啉酮稀土配合物的合成与性质

合成了新β双酮试剂1-对甲苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5(HL)及其稀土Nd(Ⅲ)、Sm(Ⅲ)、Gd(Ⅲ)配合物。根据元素分析、摩尔电导结果推出配合物的组成为[ML3(HL)].H2O。通过红外光谱、紫外-可见光谱和差热-热重分析对配合物进行了配位结构与热稳定性的研究。结果表明配体采取烯醇式羟基O及羰基O原子两种配位方式,中心离子的配位数为8。配合物摩尔电导值表明它们都是非电解质。配体的分解温度为209.6℃,配合物的分解温度升至225℃左右,热稳定性增强。     

Thermal behavior of poly(acrylic acid)–poly(vinyl pyrrolidone) and poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

Thermal analysis (TGA and DTA) of samples of PAA, PVP, PAA–PVP complexes, containing different weight fractions of PAA and ternary polymer–metal–polymer complexes, were studied. The activation energy parameters for the thermal degradation were also calculated. The study of the effect of FeCl₃, NiCl₂, and Ni(NO₃)₂ on the TGA and DTA curves of the complexes showed that the decompositions are dependent on the concentrations and the nature of the metal ions. The DTA traces of PAA–PVP complex containing FeCl₃, NiCl₂, and Ni(NO₃)₂ showed that the treatment of the complex with these metal ions causes considerable changes in the thermal decomposition of PAA–PVP complex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4049–4057, 2006     

缩聚活性的铽配合物合成、表征及其性质

通过HCl气体在无水乙醇中,与Tb4O7反应生成无水TbCl3,再与具有胺基的配体反应,合成了一种两端带有胺基的呈缩聚活性的铽配合物。用元素分析、红外光谱和紫外光谱对配合物的组成和结构进行了表征,并借摩尔电导、差热-热重和荧光光谱对配合物进行了研究。配合物的起始分解温度为230℃左右,粉末状态下具有较高的荧光强度,单色性好,在DMF中可作为聚合单体应用。     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

稀土-蛋氨酸-邻菲咯啉配合物的合成、表征及抗菌活性研究

采用冷凝回流法合成了4种新型稀土(镧、铕、钐和钕)-蛋氨酸-邻菲咯啉三元配合物,通过元素分析、EDTA-滴定、摩尔电导、红外光谱,确定了配合物的组成为RE(Met)_3phenCl_3·3H_2O(RE:La~(3+)、Eu~(3+)、Sm~(3+)、Nd~(3+);Met=L-蛋氨酸;phen=邻菲咯啉).抗菌活性的研究表明,与配体相比,稀土三元配合物对大肠杆菌(Escherichia coli)和金黄色葡萄球菌(Staphylococcus aureus)均具有更强的抑菌能力.     

铽-N-苯基邻氨基苯甲酸的合成及荧光性质

采用共沉淀法制备了稀土铽的N-苯基邻氨基苯甲酸二元配合物,同时,采用溶胶-凝胶法制备了掺杂稀土铽的N-苯基邻氨基苯甲酸二元配合物的SiO2凝胶玻璃复合发光体,研究了合成的两种配合物的热稳定性及荧光性质。结果表明:在凝胶玻璃中合成的稀土二元配合物,其热稳定性明显提高,而其特征荧光基本保持不变。     

稀土钐二元、三元配合物的合成、表征及其生物活性研究

以氯化钐、2-氨基嘧啶和钼酸钠为原料,制备了两种新型稀土钐二元、三元配合物,通过元素分析、紫外光谱、红外光谱等手段对其进行了表征,确定了二元配合物的化学组成为Sm2(AP)(H2O)2Cl3(AP=2-氨基嘧啶),三元配合物的化学组成为:Sm3(AP)(MoO4)2(CH3OH)4Cl5。抗菌结果表明,二元配合物对大肠杆菌和金黄色葡萄球菌的抑菌圈直径分别为13 mm和15 mm,三元配合物分别为13 mm和13 mm,两种配合物对大肠杆菌、金黄色葡萄球菌都有一定的抑制作用。采用MTT法对两种配合物诱导癌细胞凋亡能力做了初步研究,两种配合物的半数抑制浓度IC50在0.001~0.01 mg/mL之间,证明其具有诱导癌细胞凋亡的作用。     

含偶氮苯8-羟基喹啉稀土配合物的合成与表征

合成了三种含偶氮苯8-羟基喹啉稀土配合物,通过元素分析、红外、紫外、荧光光谱及热分析,确定了三种配合物的组成为REL3（RE=Sm,Eu,La）,三种配合物在550～650 nm都能产生荧光,峰值（λmax）分别为569,559,552 nm。     

Morphological and thermal characterization of interpolymer complexes and blends based on poly(acrylic acid) and hydroxypropylcellulose

Interpolymer complexes and blends were prepared based on poly(acrylic acid) and hydroxypropylcellulose. The structural features of polycomplexes and blends were evaluated by scanning electron microscopy and thermal analysis. It was found that the interpolymer complex obtained as a result of co‐precipitation of the polymeric components is characterized by an uniform structure which indicates the complete miscibility between the components. Films were prepared based on blends of neutralized poly(acrylic acid) and hydroxypropylcellulose. In this case the two components resulted immiscible because of the lack of intermolecular hydrogen bonding. Copyright © 2004 Society of Chemical Industry     

Grafting of poly(acrylic acid) onto cellulosic microfibers and continuous cellulose filaments and characterization

Results from the grafting of poly(acrylic acid) (PAA) onto cellulosic microfibers and continuous cellulose filaments are presented. The grafting of PAA onto cellulosic fibers offers the possibility of developing enhanced ion exchange and fluid absorbency on the fibers. The grafting of PAA was carried out with a two‐step procedure. First, vinyl‐terminated ethoxy silane was deposited on the surface of the fiber. This was followed by a grafting polymerization reaction in aqueous media of acrylic acid with different concentrations of potassium persulfate (KPS), which acted as the initiator. The percentage of grafting increased with increasing KPS concentration and reached a maximum value at a concentration of about 0.4 wt % with respect to the weight of the fiber. The grafted copolymer was characterized by Fourier transform infrared spectroscopy. Strong evidence that the grafting reaction was successful was given by the presence of a band, with a maximum at 1732 cm^?1, that was characteristic of carbonyl group absorption and was not initially present in the cellulosic fibers. The water absorption of the cellulosic microfibers grafted with PAA was three times greater than the water absorption of the nongrafted microfibers. The mechanical properties of continuous cellulose filaments did not change drastically with PAA grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 386–393, 2002     

Application of FTIR spectroscopy for structural characterization of ternary poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

The FTIR spectroscopic technique was used in the study of ternary polymer–metal complexes containing two polyelectrolytes of opposite charge and metal ions. The structure of the ternary (PAA‐Fe³⁺‐PVP) complexes was examined by following the changes in their infrared spectra. It was found that the shapes of the absorption bands of the resultant compounds are influenced by the presence of Fe³⁺. According to this result it was suggested that two types of structure which differ in the composition are formed, one of which results from the coordination of Fe³⁺ with PAA‐PVP complex and the other is due to the formation of Fe³⁺ polycarboxylate. Comparison between the spectrum of PAA‐PVP complex and those of the compounds resulted from the reaction between the two opposite charged electrolytes, PAA and PVP and each of the divalent metal chlorides NiCl₂, CoCl₂, CuCl₂, and ZnCl₂) led to the conclusion that a reaction took place between the divalent transition metal chlorides and the extent of reaction depends on the nature of metal ions and PAA‐PVP complex. The FTIR spectra of the precipitate resulted from the mixtures of PAA‐PVP and Ni(NO₃)₂ or Sr(NO₃)₂ were investigated. It was noted that the addition of Ni(NO₃)₂ or Sr(NO₃)₂ to the mixture of the electrolytes of PAA and PVP provoked appreciable changes in the characteristic spectral features of the complex resulting from the interaction of the metal ions with the polymer–polymer complex. The FTIR spectra of the precipitate resulted from the reaction between CeCl₃, ErCl₃, and LaCl₃ were also investigated. It was concluded that a reaction took place between the rare earth metals and the PPC. This means that ternary polymer–metal–polymer complexes were formed. The extent of changes in the spectral features differs from metal to metal according to the nature of metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2007