995 resultados para Tb~(3 )


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我们曾提出,电子组态具有共轭性的一对三价稀土离子,在一定条件下,会实现电子转移而产生价态变化.价态变化会明显改变材料的功能特性,因此,研究稀土元素价态变化,对新型功能材料设计具有重要意义.本工作研究了SrF_2:xEu,yTb磷光体中Eu-Tb的价态变化,发现SrF_2中,电子组态共轭的Eu~(3+)与Tb~(3+)在本实验条件下,可以实现电子转移.这一现象的发现有助于了解团相反应中稀土离子价态变化的规律.为寻找共轭稀土离子对之间实现电子转移条件提供了实验依据.

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本文首次采用溶液沉淀法合成了一系列La_4(P_2O_7)_3;Ce,Gd,Tb磷光体.经X射线分析表明,它们属于纯的La_4(P_2O_7)_3相。测定了这些化合物的激发和发射光谱、相对亮度及Ce~(3+)的发光寿命,观察到在此基质中Ce~(3+)与Gd~(3+)的光谱重叠,它们之间存在着一定的相互作用,使(La_(0.64)Ce_(0.3)Gd_(0.06)_4(P_2O_7)_3的亮度比(La_(0.7)Ce_(0.3)_4(P_2O_7)3和(La_(0.94)Gd_(0.06)_4(P_2O_7)_3有少许增加.此外,Ce~(3+)能有效地敏化Tb~(3+)~9,从而大大增强Tb~(3+)的发射.然而,Gd~(3+)与Tb~(3+)共存时存在着竞争吸收和独自发射,使(La_(0.80)Gd_(0.06)Tb_(0.14)_4(P_2O_7)_3的亮度与单掺的(La_(0.86)Tb_(0.14)_4(P_2O_7)3相比有少许降低.相应地在Ce,Gd和Tb共掺时,由于Gd~(3+)的影响,使Tb~(3+)的发射减弱,从而总的发光相对亮度有所降低。

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Ce~(3+)离子有宽而强的4f-5d吸收带,能有效地吸收能量,并形成强的宽带发射。Ce~(3+)的5d-4f跃迁是允许的电偶极子跃迁,其5d态的寿命非常短。为此Ce~(3+)可将能量有效地传递给其它离子,而成为良好的敏化剂。通常Ce~(3+)对Tb~(3+)的敏化十分有效,已有许多Ce~(3+)敏化Tb~(3+)的绿色发光材料。稀土磷酸盐是发光和激光材料的良好基质,LaPO_4:Ce,Tb已用作灯用三基色荧光粉,对不同类型稀土磷酸盐中Ce~(3+)、Tb~(3+)的发光已有不少报道,为探索新的高效

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稀土钒酸盐是很好的发光和激光材料。本文探讨了助熔剂法生长YVO_4:RE~(3+)(RE~(3+)=Pr~(3+),Sm~(3+),Tb~(3+))晶体的工艺条件。讨论了V_2O_5与Pb_2P_2O_7为助熔剂和温度对晶体成核,生长习性和缺陷的影响。并测定了晶体的结构参数。分别以V_2O_5和Pb_2P_2O_7为助熔剂进行YVO_4:RE~(3+)晶体的生长,结果表明用V_2O_5为助熔剂比用Pb_2P_2O_7为助熔剂要优越得多。以

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Ce~(3+)离子有一个宽而强的4f-5d吸收带,它能有效地吸收能量。Ce~(3+)离子的荧光寿命非常短,能将能量有效地传递给其它离子起敏化作用。对于Ce~(3+)→Tb~3+),Ce~(3+)→EU~(3+)和Ce~(2+)→Mn~(3+)的敏化作用已有许多报导,并在灯用发光材料上获得应用。Blasse等提出在Ce~(3+)敏化Tb~(3+)时。用Gd~(3+)作中间体能获得高效发光材料。由于Ce~(3+)的5d能级强烈地依赖于基质,其发射波长可以从紫外到红区,而Gd~(3+)的4f-4f跃迁的激发和发射峰值随基质的变化改变不大,因此将有可能呈现不同的Ce~(3+)-Gd~(3+)的能量转移过程。

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本文研究了以(NH_4)_2HPO_4-Li_2CO_3-MoO_3(PbF_2)为助熔剂合成 RPO_4(R=La~(3+),Ce~(3+),Tb~(3+))晶体的工艺,测试和分析了晶胞参数和晶体结构。对 CePO_4和 TbPO_4晶体的激发光谱和荧光光谱进行了讨论和分析。

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研究了NaGd_(1-x)(Eu·Tb)_xTiO_4(X=0.01~0.5)化合物的合成,结构和光谱特性,观察了Li~+,Na~+,K~+和Mn~(4+),Ge~(4+),Si~(4+)对E_u~(3+)离子~5D-~7F跃迁荧光发射的影响,讨论了Gd~(3+)→Eu~(3+),Eu~(3+)-Tb~(3+)离子间的能量转移

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The mechanism involved in the Tm(3+)((3)F(4)) -> Tb(3+)((7)F(0,1,2)) energy transfer as a function of the Tb concentration was investigated in Tm:Tb-doped germanate (GLKZ) glass. The experimental transfer rate was determined from the best fit of the (3)F(4) luminescence decay due to the Tm -> Tb energy transfer using the Burshtein model. The result showed that the 1700 nm emission from (3)F(4) can be completely quenched by 0.8 mol% of Tb(3+). As a consequence, the (7)F(3) state of Tb(3+) interacts with the (3)H(4) upper excited state of TM(3+) slighting decreasing its population. The effective amplification coefficient beta(cm(-1)) that depends on the population density difference Delta n = n((3)H(4))-n((3)F(4)) involved in the optical transition of Tm(3+) (S-band) was calculated by solving the rate equations of the system for continuous pumping with laser at 792 nm, using the Runge-Kutta numerical method including terms of fourth order. The population density inversion An as a function of Tb(3+) concentration was calculated by computational simulation for three pumping intensities, 0.2, 2.2 and 4.4 kWcm(-2). These calculations were performed using the experimental Tm -> Tb transfer rates and the optical constants of the Tm (0.1 mol%) system. It was demonstrated that 0.2 mol% of Tb(3+) propitiates best population density inversion of Tin(3+) maximizing the amplification coefficient of Tm-doped (0.1 mol%) GLKZ glass when operating as laser intensity amplification at 1.47 mu m. (C) 2007 Elsevier B.V. All rights reserved.

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Crystalline terbium-doped indium hydroxide structures were prepared by a rapid and efficient Microwave-Assisted Hydrothermal (MAH) method. Nanostructures were obtained at a low temperature. FE-SEM images confirm that these samples are composed of 3D nanostructures. XRD, optical diffuse reflectance and photoluminescence (PL) measurements were used to characterize the products. Emission spectra of terbium-doped indium hydroxide (In(OH)3:xTb 3+) samples under excitation (350.7 nm) presented broad band emission referent to the indium hydroxide matrix and 5D4 → 7F6, 5D4 → 7F 5, 5D4 → 7F4, and 5D4 → 7F3 terbium transitions at 495, 550, 590 and 627 nm, respectively. Relative intensities of the Tb 3+ emissions increased as the concentration of this ion increased from 0, 1, 2, 4 and 8 mol%, of Tb3+, but the luminescence is drastically quenched for the In(OH)3 matrix. © 2012 Elsevier B.V. All rights reserved.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Enhancement of bone mineral acquisition during growth may be a useful preventive strategy against osteoporosis. The aim of this study was to explore the lean mass, strength, and bone mineral response to a 10-month, high-impact, strength-building exercise program in 71 premenarcheal girls, aged 9–10 years. Lean body mass, total body (TB), lumbar spine (LS), proximal femur (PF), and femoral neck (FN) bone mineral were measured using the Hologic QDR 2000+ bone densitometer. Strength was assessed using a grip dynamometer and the Cybex isokinetic dynamometer (Cybex II). At baseline, no significant difference in body composition, pubertal development, calcium intake, physical activity, strength, or bone mineral existed between groups. At completion, there were again no differences in height, total body mass, pubertal development, calcium intake, or external physical activity. In contrast, the exercise group gained significantly more lean mass, less body fat content, greater shoulder, knee and grip strength, and greater TB, LS, PF, and FN BMD (exercise: TB 3.5%, LS 4.8%, PF 4.5%, and FN 12.0%) compared with the controls (controls: TB 1.2%, LS 1.2%, PF 1.3%, and FN 1.7%). TB bone mineral content (BMC), LS BMC, PF BMC, FN BMC, LS bone mineral apparent density (BMAD), and FN bone area also increased at a significantly greater rate in the exercise group compared with the controls. In multiple regression analysis, change in lean mass was the primary determinant of TB, FN, PF, and LS BMD accrual. Although a large proportion of bone mineral accrual in the premenarcheal skeleton was related to growth, an osteogenic effect was associated with exercise. These results suggest that high-impact, strength building exercise is beneficial for premenarcheal strength, lean mass gains, and bone mineral acquisition.

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Lanthanide complexes Ln(DTPAAQ)(DMF)] (1-3) (Ln - Pr (1), Eu (2), Tb (3), H(3)DTPAAQ - N, N `'-bis(3-amidoquinolyl) diethylenetriamine-N, N', N `'-triacetic acid, DMF - N, N-dimethylformamide) were studied for their structures, photophysical properties, DNA and protein binding, DNA photocleavage, photocytotoxicity and cellular internalization. The crystal structures of complexes Ln(DTPAAQ)(DMF)] (1-3) display a discrete mononuclear nine-coordinate {LnN(3)O(6)} tricapped-trigonal prism (TTP) coordination geometry. The europium and terbium complexes show strong luminescence properties in the visible region having a long luminescence lifetime (tau = 0.51-0.64 ms). The conjugated 3-aminoquinoline moieties act as efficient light harvesting antennae, which upon photoexcitation transfer their energy to Eu(III) or Tb(III) for their characteristic D-5(0) -> F-7(J) or D-5(4) -> F-7(J) f-f transitions respectively. The complexes display efficient binding affinity to DNA (K-b = 3.4 x 10(4) - 9.8 x 10(4) M-1) and BSA (KBSA = 3.03 x 10(4) - 6.57 x 10(4) M-1). Europium and terbium complexes give enhanced luminescence upon interacting with CT-DNA suggesting possible luminescence-based sensing applications for these complexes. Complexes 1-3 show moderate cleavage of supercoiled (SC) DNA to its nicked circular (NC) form on exposure to UV-A light of 312 nm involving formation of singlet oxygen (O-1(2)) and hydroxyl radicals (cOH) in type-II and photoredox pathways. Eu(III) and Tb(III) complexes exhibit remarkable photocytotoxicity with human cervical cancer cell line (HeLa) (IC50 = 20.7-28.5 mM) while remaining essentially noncytotoxic up to 150 mM in the dark. Complexes are nontoxic in nature thus suitable for designing cellular imaging agents. Fluorescence microscopy data reveal primarily cytosolic localization of the Eu(III) and Tb(III) complexes in HeLa cells.

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随着稀土的广泛开发和利用,稀土日益进入环境,并且相继发现稀土具有多种生物效应。稀土与生物小分子配体多元体系中稀土化学形态的研究正是考察稀土在人体内的分布、代谢和生物效应的关键,对阐明稀土对环境和人体健康的影响及作用机理具有十分重要的意义。本论文进行了如下几方面的研究,并取得了创新性结果。1 稀土与生物小分子三元体系研究 在模拟生理条件下研究了Pr~(3+)、Gd~(3+)、Tb~(3+)、Yb~(3+)四种稀土离子和Ca~(2+)、Zn~(2+)两种生物金属离子分别与以天冬氨酸或柠檬酸为第一配体、分别以水扬酸、精氨酸、丝氨酸、异亮氨酸和苏氨酸为第二配体的三元溶液体系。经计算机程度优化得到体系中所生成的物种类型并计算得到各物种的稳定常数。在所研究的十个体系中,只是在金属离子-天冬氨酸-精氨酸、金属离子—柠檬酸-水杨酸和金属离子-柠檬酸-精氨酸三个体系中生成了两种三元配合物(1111型和1112型或1113型),其它体系只生成了一种1112型三元配合物。重稀土配合物的稳定常数比轻稀土配合物的大。稀土配合物的稳定性明显强于钙配合物,接近或大于锌配合物的稳定常数,这表明稀土对钙有强竞争配位作用,对锌也有强竞争取代作用。以上稀土与生物小分子三元体系的研究取得了重要新结果。这些结果为考察稀土在体内的代谢、生物效应以及研究稀土对生物金属离子的拮抗、协同效应提供了重要科学依据。同时该研究也是多元体系数学模型法研究的基础。2. 金属离子生物小分子多元体系的数学模型法研究(1)对稀土与钙共存于两种生物配体(柠檬酸和精氨酸、天冬氨酸和精氨酸、柠檬酸和丝氨酸、柠檬酸和异亮氨酸、天冬氨酸和苏氨酸)的五个四元体系,经COMICS程序,利用已有二、三元配合物的稳定常数进行了计算。得到了稀土和钙的各物种随pH值变化的分布图。与三元体系相比,自由金属离子和二元配合物的含量显著增加。这表明稀土和钙之间存在着明显的竞争作用。(2)用数学模型法模拟研究了金属离子与血液中羧肽酶A的活性中心的作用。确定了Zn(II)和Tb(111)与该酶活性中心各残基的结合随pH的变化情况。当血液中稀Tb(III)的浓度较小时(与Zn(II)的浓度相近),Tb(III)对该酶活性中心的Zn(II)几乎没有影响;当Tb(III)达到较高浓度时,则能够与Zn(II)竞争活性中心各残基,从而可能影响该酶的结构和活性。(3)用数学模型法研究了人体血浆中生物小分子体系(二十种配体共存)Tb(III)和Ca(11)的分布情况及Tb(III)的存在对Ca(11)化学形态的影响。结果表明大部分铽与生物小分子配体形成多种形式的配合物,三元配合物占绝对优势。钙与铽明显不同,相当一部分的钙以自由离子形式存在,同时三元配合物也是钙的主要物种形式。模拟研究还表明当铽离子的浓度达到1E-4mol/L时,铽的存在会明显影响钙离子的物种形式及分布。以上多元体系的数学模型法研究所得创新性结果对考察稀土的分布、代谢及其生物效应和阐明稀土对钙的竞争取代作用都具有十分的重要意义。并且也进一步丰富和发展了稀土的生物无机化学。

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分别采用溶胶凝胶方法,固相合成法,燃烧法,均相沉淀法在不同的铝酸盐中研究了稀土离子的发光性质及稀土离子之间的能量传递。并对各种方法合成的稀土铝酸盐的发光性能进行比较。全新方法——均相沉淀法合成的稀土铝酸盐既克服了传统的溶胶凝胶方法中有机碳对还原气氛的影响,又能够在较低温度下,较短的时间内合成铝酸盐,克服铝酸盐合成温度高时间长的弊病。以这种方法在750 ℃,4h即可合成发光性能较好的铝酸盐磷光体。系统的合成铝酸盐MAl_2O_4:Eu~(2+), RE~(3+) (M = Mg, Ca, Sr, Ba; RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)的发光及长余辉性质,发现Pr, Nd, Dy, Ho, Er均能够有效的延长MAl_2O_4:Eu~(2+)的发光寿命,同时增强MAl_2O_4:Eu~(2+)的发光亮度。其中以Dy, Eu共掺的铝酸盐磷光体的寿命最长。对于碱土金属,虽然同属于鳞石英结构,但其晶体结构存在明显差别:Mgl_2O_4:Eu~(2+),RE~(3+)隶属于立方晶系,Ca Al_2O_4:Eu~(2+),RE~(3+)和β-SrAl_2O_4:Eu~(2+),RE~(3+)隶属于单斜晶系,Ba Al_2O_4:Eu~(2+), RE~(3+)隶属于六角晶系。所以在发光性能及长余辉性能上表现出不同的特性:Mg Al_2O_4:Eu~(2+),RE~(3+) 和Ba Al_2O_4:Eu~(2+), RE~(3+)的发光分别为480nm, 500nm, 界于Ca Al_2O_4:Eu~(2+), RE~(3+) (436 nm)和 β-SrAl_2O_4:Eu~(2+),RE~(3+) (520 nm)之间。而 Ca Al_2O_4:Eu~(2+),RE~(3+)和β-SrAl_2O_4:Eu~(2+),RE~(3+)由于同属于单斜晶系,所以其发光满足原子序数的变化规律:当某一原子取代较小的其他原子时,发光波长向短波移动。而且Ca Al_2O_4:Eu~(2+),RE~(3+)和β-SrAl_2O_4:Eu~(2+),RE~(3+)都具有较强的发光及余辉。发现新型长余辉发光物质碱土铝酸盐MA:Eu~(2+),RE~(3+),波长位于489nm,是一种发光和余辉都极强的发光材料。而且碱土铝酸盐MA:Eu~(2+),RE~(3+)能与β-SrAl_2O_4:Eu~(2+),RE~(3+)生成非常有效的混晶化合物,从而使其发光在489nm~520 nm的波长范围内移动而不影响化合物的发光性能。研究了SrGdAlO_4:RE~(3+) (RE = Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu)的发光现象,观察到SrGdAlO_4:RE~(3+) (RE = Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er)的特征发光,由于Tm, Yb, Lu 在可见区无吸收,所以观察不到它们的发光。讨论并研究了SrGdAlO_4:RE~(3+) 体系的Gd~(3+) → Gd~(3+),Gd~(3+) → RE~(3+)的能量传递机理,总结了RE~(3+)对Gd~(3+)的激发能的俘获速率次序依次为: Eu > Tb >Er > Dy > Sm > Ho > Nd,能量传递主要是通过偶极-偶极相互作用实现的。观察到SrGdAlO_4:Tb~(3+)长余辉发光。

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利用溶胶-凝胶法制备了SiO_2、TiO_2等单组份凝胶玻璃及二者混合的双组份二元凝胶玻璃。对其中溶胶的形成、溶胶向凝胶的转化过程及最终凝胶玻璃的形成进行了大量系统的研究。稀土(Tb~(3+)、Eu~(3+))配合物分别以预掺杂法、原位(in-situ)掺杂法及原位两步水解法等方法掺入溶胶中,用旋转涂覆法(spin-coating method)制成发光薄膜。利用荧光光谱、红外光谱、X射线衍射分析等现代谱学方法对薄膜的性能进行了分析。由于稀土Eu~(3+)离子的~5D_0→~7F_2跃迁是对环境变化比较敏感的跃迁超灵敏跃迁,相应于这些跃迁的谱线强度随着环境的不同可改变2-4倍,故将Eu~(3+)离子作为荧光探针引入TiO_2凝胶玻璃中来研究TiO_2凝胶形成中的水解、缩聚过程。差热一热重分析表明在400 ℃左右TiO_2凝胶发生了由无定型向锐钛矿型的晶型的转变,在不同温度下处理的TiO_2凝胶的XRD曲线也可得到同样的结论。当温度达到800 ℃时观察到了金红石相的微小的衍射峰。从Eu~(3+)离子的荧光光谱可以看出对应于610 nm的~5D_0→~7F_2的跃迁强度(I_2)和590 nm的~5D_0→~7F_1的跃迁强度(I_1)随着热处理温度的升高而逐渐增强,说明随着处理温度升高,凝胶中水分子不断挥发,热处理过程中的羟基含量由于缩聚反应的不断进行而逐渐减少。~5D_0→~7F_1的跃迁属于磁偶极跃迁,发射强度I_1变化与环境变化无关。定义两个发射强度的比值R(R=I_2/I_1),由R值的变化可以看出,TiO_2湿凝胶时Eu~(3+)离子与水成水合离子,干凝胶中水合离子逐渐被(Ti-O)_nEu键所取代,Eu~(3+)离子逐渐进入凝胶网状结构中。同时掺入Al~(3+)离子的凝胶中Eu~(3+)的发光强度要大于不含Al~(3+)离子的凝胶中Eu~(3+)的发光强 度,因为Eu~(3+)离子的聚集对荧光有猝灭作用,掺入Al~(3+)离子之后由于其对Eu~(3+)离子的分散作用使得跃迁强度大大增强。采用预掺杂法;原位掺杂法;原位两步水解法制备了稀土Eu~(3+)、Tb~(3+)的羧酸类配合物,2-2‘联吡啶,1,10-邻菲咯啉,β-二酮类等有机配合物掺杂的溶胶-凝胶发光薄膜。双掺Tb~(3+)和苯甲酸的凝胶荧光薄膜的红外分析结果可以看出,制得的凝胶薄膜的红外光谱图与SiO_2凝胶粉末的红外光谱图几乎一致,Tb~(3+)及有机配体掺入凝胶后配合物没有明显的特征振动吸收峰。说明配合物进入凝胶网状结构中,其振动被缩聚反应形成的微小孔隙结构所限制,没能观察到明显的吸收峰。由几种双掺稀土羧酸配合物的SiO_2凝胶薄膜的激发光谱可以看出,当以稀土Eu~(3+)离子或Tb~(3+)离子的特征发射波长监控时,得到的激发谱均为260 nm-350 nm范围内的宽带代替了稀土离子的特征窄带激发光谱,可以判断在凝胶薄膜中已经形成了配合物。而且双掺凝胶薄膜发射峰值比单掺稀土离子的凝胶薄膜发光强度高几个数量级。同时将薄膜在一定温度下进行热处理发现,对于双掺稀土和羧酸配体的凝胶薄膜,50 ℃时发射光谱无明显的发射峰,而随着热处理温度的逐渐升高出现发射峰并且强度逐渐增强,热处理超过100 ℃时发射峰的强度又有所降低。说明温度的升高使凝胶环境向着有利于稀土配合物形成的方向转变,因为两步水解过程中加入的六次甲基四胺会随着温度升高而逐渐分解出OH~-而仗凝胶环境pH值升高;另一方面,由于分子水和HCl的不断挥发也能提高凝胶环境的pH值,从而使配合物的形成反应更加完全。超过120 ℃后,接近配体的熔点(苯甲酸熔点129 ℃),由于薄膜相当薄使配体的逐渐分解,荧光逐渐减弱;经175 ℃处理后,荧光几乎消失。除了羧酸配合物外还制备了稀土Tb~(3+) (Eu~(3+))与2-2‘联吡啶(邻菲咯啉)、TTA等二元配合物掺杂的溶胶-凝胶发光薄膜。凝胶薄膜的发光强度与相应的纯配合物薄膜相比由于凝胶的独特网状结构而有了较大的提高,通过荧光光谱和荧光寿命的比较均可以得出这样的结论。对凝胶薄膜和纯配合物/PVB薄膜的热稳定性比较可以看出,溶胶-凝胶发光薄膜的荧光强度随温度升高而降低,但与配合物的PVB薄膜的相比,仍显示了一定的热稳定性,在温度超过配合物的分解温度后仍显示出一定的发光强度,而纯配合物/PVB薄膜中配合物的荧光此时几乎完全消失。除了SiO_2凝胶之外,还制备和研究了TiO_2凝胶以及TiO_2-SiO_2复合凝胶作为基质的发光薄膜,发现在TiO_2凝胶中配合物未能象在SiO_2中那样显示出良好的发光性能,可能是因为作为过渡金属钛由于有d轨道与掺入其中的配体作用参与成键,影响了配体与稀土离子之间的能量转移。本论文中还将在光学领域中有重要作用的染料,例如荧光素(FL)引人TiO_2凝胶中,研究了FL在凝胶中的发光性质,对比了FL掺入TiO_2、TiO_2-SiO_2凝胶前后的吸收光谱、荧光光谱的变化。结果表明吸收峰有了较为明显的位移;荧光发射光谱吸收峰位置也有了较大的红移,这可能是由于凝胶的网状结构及孔道内的Ti-OH键等对染料影响的结果。