Luminescent Sensing with Quantum Dots

Summary This review highlights recent advances in the use of quantum dots (QD’s) as luminescent sensors. The bulk of the study concentrates on systems that possess organic ligands bound to the surface of QD’s. These ligands vary from low molecular weight thiols to larger molecules such as maltose binding protein. All have one thing in common: when a target analyte binds to the ligand/receptor, a perturbation of the system occurs, that registers itself as a change in the luminescence intensity of the QD. Two main mechanisms are prevalent in controlling the luminescent intensity in such systems. The first is Photoinduced Electron Transfer (PET) and the second energy transfer. This review looks at current sensors that operate by using these mechanisms. Two component systems are also investigated where a quencher is first added to a solution of the QD, followed by addition of the target analyte that interacts with the quencher to influence the luminescence intensity.     

Determination of lutetium by fluorimetry, using BPMPHD and CTMAB

Lutetium(III) forms an association compound with a new synthetic reagent, 1,6-bi(1-phenyl-3-methyl-5-pyrazolone-4)hexandione (BPMPHD), and cetyltrimethylammonium bromide (CTMAB). The compound enhances the natural fluorescence of BPMPHD remarkably, upon which a new fluorescence method was developed for determining lutetium in rare earth (RE) samples. The determination range was 1.80 × 10^–7–8.8 × 10^–6 g/ml. The determination limit was 29 ng/ml. The composition of the ion associate was [Lu(BPMPHD)₂]–CTMAB⁺.     

Synthesis and red luminescence of Pr-doped CaTiO3 nanophosphor from polymer precursor

Uniform and sphere-like nanoparticles of crystalline Pr³⁺-doped CaTiO₃ have been prepared from complex polymer precursor at 600°C, in which, metal atoms are previously dispersed by citric acid in ethylene glycol solvent. The decomposition process of the precursor, crystallization, and particle sizes of CaTiO₃ have been investigated by using thermal analysis, powder X-ray diffraction and transmission electron microscopy. Diffuse reflectance spectra, photoluminescence and decay curve indicate that a strong red emission located at the nearly NTCS “ideal red” site is deduced from the energy transfer from the band gap absorption to doping Pr³⁺ ions. The thermoluminescence curves exhibit that a potential long phosphorescent material based on Pr³⁺-doped CaTiO₃ will be explored in future.     

Vibronic intensities in centrosymmetric coordination compounds of the rare earths Part II. A vibronic crystal field-closure-ligand polarisation model and applications to the PrCl6 and UBr6 complex ions in octahedral symmetry

A symmetry adapted formalism to evaluate the vibronic intensities induced by the ungerade vibrational modes in centrosymmetric coordination compounds of the rare earths is put forward and applied to several selected electronic transitions of the PrCl³⁻₆ and UCl²⁻₆ complex ions in octahedral symmetry. This current model is based upon a modified symmetry adapted version of the combined vibronic crystal field-closure-ligand polarisation approach. This model differs from that developed in Part I of this series, in that for the vibronic crystal field contribution to the total transition dipole moment, the closure procedure is employed rather than the utilisation of a truncated basis set for the central metal intermediate electronic states. A criterion is introduced to choose an appropriate set of phases for both the electronic and the vibrational coordinates so that to ensure the right sign for the interference term (which couples together both the vibronic crystal field and the vibronic ligand polarisation contributions to the total transition dipole moment). We have focused our attention on the modulation of the intermolecular force field and a version of a modified general valence force field has been adopted. The reasons for using this formalism rather than the superposition model (SM) are fully discussed in the text. Finally, it is shown that the agreement with experiment is satisfactory for most of the components of the transitions studied, despite the apparent simplicity of our model calculation. General master equations applicable to any f^N electronic configurations are derived to show the utility and flexibility of this current formalism.     

新型陶瓷材料的光激励发光性质研究

针对以往电子俘获光存储材料存在的问题，利用高温固相反应发制备了一种Eu^2 掺杂的氟氧化物玻璃陶瓷，研究表明在该材料中具有光激励发光(PSL)特性，并可用于电子俘获光存储。XRD分析表明该材料含有大量的BaF2微晶。根据其与BaF2相似的发光特性，推断玻璃陶瓷的PSL有可能来源于微晶中Eu^2 的5d-4f发射。但是决定光激励发光过程中的电子(空穴)陷阱的存在方式、电子迁移途径都有待进一步探讨的问题。与传统的BaFCl：Eu相比，这种材料的光激励发光衰减速度较慢。     

稀土掺杂的(K, Sr)Cl·SiO2复合凝胶的荧光性能

采用sol gel法制备了单掺铕及共掺铕、铈的(K,Sr)Cl·SiO2复合凝胶,研究了复合凝胶的荧光性能。根据荧光测试结果,复合凝胶中,Eu3+在没有还原剂的作用下,可以与基质作用形成还原态的Eu2+,复合凝胶表现出相应的Eu2+荧光性能;研究认为,Ce3+,Eu3+共掺杂时,复合凝胶激发光谱与发射光谱峰位基本不变,但强度有所不同。330nm处的激发光谱明显增强,且发射光谱随Ce3+的掺杂量增加而增强。当Ce3+掺杂浓度为3.0%(原子分数)时,复合凝胶具有最大的荧光发射强度,表明Ce3+具有很好的敏化作用。在Ce3+,Eu3+共掺杂复合凝胶体系中,复合凝胶荧光强度增大的原因既可能是电子转移过程,也可能是Ce3+→Eu2+的能量传递过程所致。     

Chemical-effect variation of Kβ/Kα X-ray intensity ratios in 3d elements

Chemical effects on Kβ/Kα X-ray intensity ratios for some Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn compounds are studied experimentally. The X-ray spectra were measured by using a Si (Li) solid state detector with high resolution. The vacancies were produced by heavily filtered ²⁴¹Am gamma rays. It is found that the Kβ/Kα X-ray intensity ratios measured with compounds deviated up to 43% from the corresponding values of the pure elements. The values for pure elements are compared with the other experimental and with theoretical values.     

YPxV1—xO4（0≤x≤1）：Dy^3＋的合成及其光谱性质的研究

本文报道了不同组成的ＹＰｘＶ１－ｘＯ４（０≤ｘ≤１）：Ｄｙ＾３＋的合成和结构。ＹＰｘＶ１－ｘＯ４（０≤ｘ≤１）为四方晶系，晶胞参数随ｘ的增大呈线性减小。基质的Ｓｔｏｋｅｓ位移随ｘ的增大逐渐变大，而激发光谱峰值则向短波方向移动。在ＹＰｘＶ１－ｘＯ４：０．００６Ｄｙ＾３＋体系中，ｘ＞０．４时出现的基质发射是由ＰＯ＾３－４引起的。基质及Ｄｙ＾３＋的发光效率和Ｄｙ＾３＋的发光强度的黄蓝比均与ｘ有关。同时探     

Eu（TTA）3·1／2（4，4′－bipyN_2O_2）配合物的发光光谱

在７７Ｋ下测定了Ｅｕ（ＴＴＡ）３·１／２（４，４′－ｂｉｐｙＮ２Ｏ２）配合物的激发光谱、发光光谱和时间分辨光谱。光谱数据表明，在标题配合物中存在化学环境不同的两种Ｅｕ３＋格位，但它们的局部对称性都属于Ｃ２Ｖ点群，这可能表明该配合物的激发态电子结构稍有不同     

助熔剂对Y3Al5O12：Ce荧光粉性能的影响

在还原气氛下采用高温固相反应法合成了白光LED用黄色荧光粉Y3Al5O12:Ce(YAG:Ce)研究了助熔剂对YAG：Ce荧光粉发光特性的影响，。XRD的测量结果表明加入合适的助熔剂有利于YAG:Ce荧光粉的晶化，并且不引入杂相，选择BaF2和H3BO3同时使用效果要好于单独使用一种助熔剂，助熔剂的加入可增大YAG：Ce荧光粉的激发和发射光谱强度，并能有效降低荧光粉的中心粒径（D50）控制粉体的粒径分布，适用于白光LED的制造。