Synthesis and characterization of a main‐chain‐type conjugated copolymer containing rare earth with photocrosslinkable group

In this article, we report the design, synthesis, and characterization of a new main‐chain‐type rare earth‐containing conjugated polymer with photocrosslinkable group. The polymer is crosslinked photochemically by the addition of a photoinitiator to yield an absolute insoluble network. The optical properties of the resulting conjugated polymer were characterized in solution, film state, and after photocrosslinking. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 388–394, 2007.     

Novel cationic rare earth metal alkyl catalysts for precise olefin polymerization

This mini‐review provides recent progress in the synthesis of rare earth metal dialkyl complexes and their application as highly efficient and regio‐/stereoselective catalysts in the coordination‐insertion (co)polymerization of olefins such as styrene, isoprene, 1,3‐cyclohexadiene, and ocimene. Through modifying the coordination atom, the ligand skeleton, and the substitutent on the skeleton of the chelating ligand, tuning the electron density and the steric environment around the rare earth metal center, the precise control of the activity and regio‐/stereoselectivity of the (co)polymerization as well as the comonomer incorporation and sequence distribution of the resulting copolymers are achieved. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2271–2280     

Synthesis and characterization of rare earth complexes with Phthalaldehyde-lysine Schiff base

Ten new rare earth complexes with Schiff base (HL) derived from phthalaldehyde with two-CHO groups and lysine, which has unsymmetrical α-and ε--NH₂ groups, were synthesized and characterized by elemental analysis, TG-DTA analysis, UV-Vis, IR, and ¹H NMR spectra. They were confirmed to be as LnL₂(NO₃)·4H₂O (Ln=La, Pr, Nd, Sm, Y) and LnL₂(NO₃)·3H₂O (Ln=Gd, Tb, Dy, Er, Yb), respectively. Furthermore, their coordination mechanism, spectral properties and probable molecular structures were also discussed. __________ Translated from Journal of Zhejiang University (Science Edition), 2005, 32 (5) (in Chinese)     

Synthesis and characterization of highly random copolymer of ϵ-caprolactone and D,L-lactide using rare earth catalyst

Highly random copolymers of ϵ-caprolactone (CL) and D ,L -lactide (LA) were synthesized by a new catalyst system, rare earth chloride–propylene oxide (PO) system. In the presence of propylene oxide, all rare earth chlorides tested are highly effective for the copolymerization. The influences of reaction conditions on the copolymerization catalyzed by the NdCl₃-5PO system have been investigated in detail. The reactivity ratios of ϵ-caprolactone and D ,L -lactide were determined and show that the copolymerization with this new rare earth catalyst is closer to ideal copolymerization than reported for other catalysts. The microstructure of copolymer analyzed by ¹³C-NMR shows that the monomer units in the copolymer is near to completely random distribution with a short average monomer sequence length. The DSC measurement confirms the high randomness of the chain structure. The mechanism studied by NMR indicates that the rare earth alkoxide generated by the reaction of rare earth chloride with propylene oxide initiates the copolymerization, and then proceeds via a “coordination-insertion” mechanism with acyl-oxygen bond cleavage of CL and LA. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of fluorescent cotton cellulose labeled with norfloxacin

To expand the application of cellulose in the field of fluorescence techniques, the cotton cellulose was labeled with norfloxacin (Cell-NF) via a three-step reaction, involving alkali treatment, epoxy activation, and opening of the epoxy rings with norfloxacin molecules. And the coordination complexes of Cell-NF with rare earth ions terbium (Cell-NF-Tb) and europium (Cell-NF-Eu) were obtained. The products were detected by IR, TG, XPS, UV and fluorescence spectra. Results showed that the norfloxacin content of the labeled cellulose was about 6.73 w% and the start temperature of decomposition of the Cell-NF was raised by 40°C compared with the stock cotton cellulose. When excited at 340 nm, the Cell-NF, Cell-NF-Tb, and Cell-NF-Eu in the solid state could emit violet (430 nm), green (549 nm) and red (620 nm) light, respectively.     

银钨硼三元杂多配合物的合成、稀土多元渗及其导电性

用直接法合成了未见文献报道的具有Keggin结构的以Ag作为第二配位离子的钨硼杂多配合物,利用ICP,IR,XRD和XPS等对其结构进行了表征.以Gd作为渗入元素对其进行化学气相扩渗,借助IR,TG-DTA,XPS和XRD对配合物扩渗前后的结构及稳定性进行了对比研究.导电性的测试表明:室温下,扩渗后试样的电导率提高了约103倍,且热稳定性也有所提高,是一种受温度变化影响较小的导电材料,为制备可实用的导电材料提供了一条新途径.     

一种含稀土阳离子的多金属氧酸盐二聚体的合成及晶体结构(英文)

以Na7[α-PW11O39].nH2O,Sm(NO3)3.6H2O和(CH3)4NCl为原料,利用常规的水溶液方法合成了一例新的2∶2型二聚单缺位Keggin结构多金属氧酸盐稀土衍生物[(CH3)4N]6[(α-PW11O39H)Sm(H2O)3]2.9H2O(1);利用X射线单晶衍射表征了其晶体结构.结果表明,该二聚体属单斜晶系,P2(1)/c空间群,晶胞参数为:a=1.300 8(10)nm,b=2.219 0(17)nm,c=2.097 0(16)nm,β=100.992(16),Z=2,R1=0.074 6,wR2=0.182 6.二聚阴离子[{(α-PW11O39H)Sm(H2O)4}2]6-由2个[α-PW11O39H]6-缺位阴离子通过2个[Sm(H2O)4]3+配离子连接形成,Sm3+离子占据[α-PW11O39H]6-阴离子的缺位位置并取八配位单四方反棱柱构型,相邻的2个单取代阴离子[α-PW11O39H]6-通过2个Sm-Ot-W桥连成二聚物.     

双水杨醛缩乙二胺稀土配合物的合成及表征

近年来对近红外发光稀土配合物的研究逐渐引起人们的重视[1 7]。本文合成了双水杨醛缩乙二胺(Ｃ16Ｈ16Ｎ2Ｏ2,Ｈ2Ｌ)合Ｎｄ(Ⅲ)、Ｇｄ(Ⅲ)、Ｙｂ(Ⅲ)配合物,报道该Ｓｈｉｆｆ碱配体对Ｎｄ(Ⅲ)、Ｙｂ(Ⅲ)离子近红外发光的敏化作用。1　实验部分浓盐酸和盐酸羟胺溶解稀土氧化物(广东珠江冶炼厂产品,纯度大于99 95%)并将所得溶液蒸至近干,得到相应的稀土氯化物,加入无水乙醇溶解得ＬｎＣｌ3(Ｌｎ=Ｎｄ,Ｙｂ,Ｇｄ),回流条件下将稀土氯化物乙醇溶液逐滴加入双水杨醛缩乙二胺[8]乙醇溶液中,稀土氯化物和配体为1∶2(Ｖ∶Ｖ)。回流反应10ｈ后得…     

Synthesis and characterization of star oligo/poly(2,2‐dimethyltrimethylene carbonate)s containing cholic acid moieties

Star oligo/poly(2,2‐dimethyltrimethylene carbonate)s containing cholic acid moieties were synthesized through the ring‐opening polymerization of 2,2‐dimethyltrimethylene carbonate (DTC) initiated by cholic acid with hydroxyl groups. Through the control of the feed ratio of the initiator cholic acid to the monomer DTC, a series of star oligomers/polymers with different molecular weights were obtained. The star oligomers/polymers were characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, combined size exclusion chromatography/multi‐angle laser light scattering analysis, wide‐angle X‐ray scattering, polarizing light microscopy, and differential scanning calorimetry. Compared with linear poly(2,2‐dimethyltrimethylene carbonate), these star oligo/poly(2,2‐dimethyltrimethylene carbonate)s had much faster hydrolytic degradation rates. With one of the star oligomers/polymers, a microsphere drug‐delivery system of a submicrometer size was fabricated with a very convenient ultrasonic dispersion method that did not involve toxic organic solvents. The in vitro drug release was studied. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6688‐6696, 2006     

1H-苯并三唑-1-乙酸稀土配合物的合成、表征及性质

溶液法合成了铕、铽与1H-苯并三唑-1-乙酸及1,10-邻菲啰啉的稀土配合物。通过元素分析、稀土配位滴定、摩尔电导、红外光谱、紫外光谱等手段对配合物进行了表征。结果表明,配合物的可能组成为Ln(L)3phen(Ln=Eu(III),Tb(III);HL=1H-苯并三唑-1-乙酸,Hbtaa;phen=1,10-邻菲啰啉)。利用荧光光谱、热分析和电化学方法讨论了配合物性质。荧光光谱表明配合物均有较好的发光性能。     

Synthesis and characterization of bipolar copolymers containing oxadiazole and carbazole pendant groups and their application to electroluminescent devices

A series of random copolymers POC10{Poly(2,5‐bis[(5‐decyloxy‐phenyl)‐1,3,4‐oxadiazole]styrene)}‐co‐Poly(N‐vinylcarbazole) (PVK) with different nvk content were synthesized through common radical polymerization and were incorporated into light emitting diodes as emitting layers. The structures and properties of the copolymers were characterized and evaluated by GPC, TGA, DSC, UV, PL, CV, and EL analyses. All the polymers enjoy high thermal stability. Cyclic voltammetry revealed that, with the incorporation of N‐vinylcarbazole to the copolymer, these copolymers had high‐lying HOMO energy values, which facilitated hole injection. PL peaks in the film show blue‐shift compared with those in solutions and fluorescent quantum efficiency decreased with the nvk content increasing, which supported the efficient energy transfer from nvk units to the oxadiazole units. Single‐layer LEDs with the configuration of ITO/PEDOT/PC10‐nvk/Mg:Ag/Ag were fabricated, which emit a blue light around 440 and 490 nm with a maximum brightness of 675.3 cd/m² and luminous efficiency of 0.108 cd/A. Moreover, we fabricated electrophosphorescent device from bipolar transport copolymer PC10‐nvk4 as host material and an orange‐light‐emitting iridium phosphor IrMDPP as guest. The maximum luminous efficiency of 0.548 cd/A was obtained. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5452–5460, 2008     

Synthesis and near infrared properties of rare earth ionomers

Fully exchanged, anhydrous ionomers of ethylene-co-acrylic acid (EAA) copolymers and ethylene-co-methacrylic acid (EMAA) copolymers containing Dy⁺³, Er⁺³, Sm⁺³, Tb⁺³, Tm⁺³, and Yb⁺³, and mixtures of them, were synthesized and studied in the near infrared region by reflection and Fourier Transform Laser Raman spectroscopies. The EAA copolymers ranged from 1.4 to 8.7 mol % acid and the EMAA copolymers were 7.3 and 16.2 mol % acid. The ionomers were shown to be essentially free of carboxylic acid groups, water, or other forms containing O (SINGLE BOND) H groups and were characterized by infrared and other methods. They are light and heat stable, and become thermoplastic and moldable at ca. 220°C under pressure. When excited at 1.064 μ with a Nd: YAG laser, these ionomers exhibit novel, lanthanide-dependent near infrared luminescence and strong Raman scattering in the near infrared region. The strongest luminescence is observed with Sm⁺³ ionomers. The Dy⁺³ ionomer Raman-shifts this source to emit light most strongly in the 1.53–1.55 μ range where the ionomer also transmits light well. © 1996 John Wiley & Sons, Inc.     

Synthesis,characterization and properties of polycarbonate containing carboxyl side groups

Diphenolic Acid, DPA [bis(4-hydroxyphenyl)pentanoic acid] can be made from cellulose-rich waste. The t-butyl ester was converted to homo- and copolycar- bonates (with bis-phenol-A, BPA). Deblocking the ester yielded polycarbonates with pendent carboxyl groups that exhibit all the properties of polyelectrolytes and retain solubility in aqueous base without degradation for long periods.     

稀土芦丁配合物的合成、表征及荧光性质和抑菌活性的研究

以稀土金属(Ⅲ)氯化物和芦丁为原料,在乙醇溶液中(pH=7~8)合成了六种稀土芦丁配合物,通过元素分析、IR、UV、热重-差热分析、摩尔电导率的测定对配合物进行了表征,确定了配合物的组成,分析了配合物的热稳定性和热分解行为。同时初步研究了配合物在室温下的荧光性质,结果显示配合物Na5SmLCl7.6H2O(L=C27H29O16)表现出相应的Sm(Ⅲ)离子的特征发射。并研究了配合物的抑菌活性,抑菌活性试验表明六种配合物具有选择性抑菌性能。     

燃烧合成法制备稀土氧化物纳米粉

本文采用硝酸盐 甘氨酸体系合成Ｙ2 Ｏ3、ＣｅＯ2 、Ｎｄ2 Ｏ3、Ｐｒ6 Ｏ11、Ｓｍ2 Ｏ3纳米粉 ,并研究了后三者在潮湿空气中的化学稳定性。其ＩＲ谱随着颗粒尺寸的减少 ,Ｙ Ｏ振动峰发生红移 ,同时谱峰强烈展宽[1,2 ] 。1　仪器及实验ＲｉｇａｋｕＤ/ｍａｘγＡ转靶衍射仪 ,ＨｉｔａｃｈｉＨ 80 0ＴＥＭＳＸ 1 70ＦＴＩＲ光谱仪 ,ＲｉｇａｋｕＰＴＣ 1 0ＡＴＧ ＤＲＡ分析仪。制备时所用前驱物均为水合稀土硝酸盐 ,其中Ｃｅ(ＮＯ3) 3·6Ｈ2 Ｏ为分析纯商用试剂 (纯度为99 99% ) ,其他水合稀土硝酸盐则参照文献[3,4 ] 分别由高纯稀土氧化物…     

稀土元素与NEB二元配合物的pH电位法分析

氨三乙氧基三苯甲酸(ＮＥＢ)(ＮＥＢ·ＨＣｌ的分子结构式见下图)作为有立体选择性的配体,它与铀酰离子ＵＯ2(Ⅱ)配位作用已有报导[1]。在对ＮＥＢ质子化常数及二元体系Ｍ(Ⅱ)-ＮＥＢ·ＨＣｌ(Ｍ=Ｃｄ、Ｃｏ、Ｎｉ、Ｃｕ和Ｚｎ)配合物的稳定常数测定的基础上[2],本文在25℃及离子强度为0 2ｍｏｌ/ＬＫＮＯ3的条件下,用精密ｐＨ电位法考察二元体系ＲＥ(ＩＩＩ)—ＮＥＢ(ＲＥ=Ｌａ→Ｎｄ,Ｓｍ→Ｌｕ,Ｙ)中存在的配合物物种及其稳定常数。ＮＥＢ·ＨＣｌ结构式1　实验部分1 1　试剂和仪器ＮＥＢ·ＨＣｌ(Ｈ3Ｌ·ＨＣｌ,Ｌ3-=Ｃ27Ｈ24ＮＯ9)…     

N,N'-双(2-吡啶甲酰胺)-1,2-乙烷双核稀土配合物的合成及与DNA的相互作用

合成了十种稀土元素(La、Ce、Pr、Nd、Dy、Ho、Er、Tm、Yb、Lu)与N,N-双(2-吡啶甲酰胺)-1,2-乙烷(H2L)的配合物。经元素分析、热重分析、摩尔电导、IR、UV及1HNMR表征,确定配合物的组成为:[Ln2(H2L)3(NO3)2](NO3)4.nH2O,(其中Ln=La、Ce、Pr、Nd,n=0;Ln=Dy、Ho、Er、Tm、Yb、Lu,n=3),其中配体H2L中酰胺羰基氧和吡啶氮分别与稀土离子配位,硝酸根为双齿配体。通过光谱法对配合物与脱氧核糖核酸(DNA)的作用进行了初步研究,得到配合物与DNA的结合常数为1.6×104~2.3×104。     

Synthesis and thermal decomposition of some rare earth tetramethylammonium double sulphates

When reaction mixtures of rare earth(III) sulphates and tetramethylammonium sulphate in molar ratios of from 1∶4 to 1∶12 were evaporated at ambient temperature and the concentrated reaction mixture was treated with ethanol, double sulphates with general empirical formula (CH₃)₄NLn(SO₄)₂·2H₂O (Ln=Ho?Lu and Y) were obtained as reaction products. The crystalline products were identified by quantitative analysis, X-ray powder diffraction patterns and TG, DTG and DTA analysis. They were found to be isostructural. Their thermal decomposition took place in three stages. The temperature range of the dehydration mainly decreased from Ho to Lu. The thermal decomposition in the second and third stages occurred with many thermal events. As final product, Ln₂O(SO₄)₂ was obtained.     

Fabrication of fluorescent holographic micropatterns based on the rare earth complexes using azobenzene‐containing poly(aryl ether)s as macromolecular ligands

In this work, on the basis of photoinduced surface relief gratings (SRGs) with the rare earth complexes using azo‐polymers as macromolecular ligands, a series of novel materials for fabricating rewritable fluorescent two‐dimensional micropatterns, whose color can be easily adjusted by changing the species of the rare earth ions, are demonstrated. The rare earth complexes are prepared using a series of poly(aryl ether)s containing azobenzene chromophores and carboxyl group as macromolecular ligands and 1,10‐phenanthroline as co‐ligands. The fluorescence properties of the rare earth complexes and the influence of the contents of azobenzene chromophores on the fluorescent intensity are investigated by means of fluorescence excitation and emission spectroscopy. By exposing the films of the rare earth complexes to an interference pattern laser beam, SRGs can be formed on the films. Under the excitation, fluorescent patterns of the SRGs can be observed by the measurement of fluorescence microscopy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 936–943     

Synthesis,characterization, spectroscopy and thermal analysis of rare earth picrate complexes with <Emphasis Type="Italic">L</Emphasis>-leucine

Rare earth picrate complexes with L-leucine (Leu) were synthesized and characterized. Elemental analysis (CHN), EDTA titrations and thermogravimetric data suggest a general formula RE(pic)₃2Leu⋅5H₂O (RE=La–Lu, Y and pic=picrate). IR spectra indicate the presence of water and suggest that L-leucine is coordinated to the central ion through the nitrogen of the aminogroup. The absorption spectrum of the solid Nd compound indicates that the metal-ligand bonds show a weak covalent character. Emission spectra and biexponential behavior of the luminescence decay of the Eu compound suggest the existence of polymeric species. Thermal analysis results indicate that all the compounds present a similar behavior, with five major thermal decomposition steps. The final products are rare earth oxides. A slow heating rate is necessary to observe all decomposition steps.