Synthesis and Luminescent Properties of Lanthanide Complexes with a Novel Multipodal Ligand

Solid complexes of lanthanide nitrates, picrates and perchlorates with a novel multipodal ligand, 1,2,4,5-tetramethyl-3,6-bis{N,N-bis[((2′-benzylaminoformyl)phenoxyl)ethyl]-aminomethyl}-benzene (L) have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Eu and Tb complexes in solid state were investigated. Under the excitation of UV light, these complexes exhibited characteristic emission of central metal ions. The lowest triplet state energy level T₁ of this ligand matches better to the lowest resonance energy level of Tb(III) than to Eu(III) ion. The influence of the counter anion on the luminescent intensity was also discussed.     

Singlet Oxygen Quantum Yield Determination for a Fluorene-Based Two-Photon Photosensitizer

The quantum yield, Φ_Δ, of singlet oxygen generation under two-photon excitation has been determined for a fluorene derivative. A photochemical method was developed using 1,3-diphenylisobenzofuran (DPBF), a chemical quencher of ¹O₂, and 2-(9,9-didecyl-7-nitrofluoren-2-yl)benzothiazole (1) as a two-photon photosensitizer (PS). The photochemical kinetics of the quencher was measured by two different fluorescence methods. Fluorene 1 exhibited relatively high singlet oxygen quantum yield, Φ_Δ ≈ 0.4 ± 0.1, and had a two-photon absorption cross-section of 28 ± 5 GM. Thus, 1 may have potential for use as a two-photon PS in the near-IR spectral region for biomedical applications.     

Preparation, Crystal Structures and Luminescent Properties of Terbium and Europium Complexes with a New Amino-Alkenone Type Ligand

Solid complexes of terbium and europium nitrates with an amino-alkenone type ligand, 1-[2-(6-methylpyridin-2-ylamino)-5,6-dihydro-4H-pyran-3-yl]ethanone (L) have been prepared and characterized by elemental analysis, conductivity measurements, and IR spectra. The crystal and molecular structures of the complexes [TbL₂(NO₃)₃(H₂O)]·CHCl₃ (1) and [EuL₂(NO₃)₃(H₂O)]·CH₃CO₂C₂H₅ (2) have been determined by single crystal X-ray diffraction. And the coordination spheres of the complexes are similar. At the same time, the luminescent properties of the Tb³⁺ complex in solid state and in solvents were investigated at room temperature. Under the excitation of UV light, Tb(III) complex exhibited characteristic emissions but not for the Eu(III) complex. The lowest triplet state energy level of the ligand in the complex matches better to the resonance level of Tb(III) than Eu(III) ion.     

Luminescent coolants for solid-state lasers

Solutions of 13 fluorescent dyes have been used as energy transfer agents in place of the normal coolant of a Nd-YAG laser. Dye mixtures were used in a few cases where incomplete absorption of flashlamp pump energy was observed. Improvements of over 100% in laser output were observed for some dyes having a long Stokes shift when tested at both a low-input energy and a low-pulse rate. However, the absolute improvement in laser output for these dye solutions was small, and the improvement could be obtained almost as well by merely increasing the pulse rate. Various factors associated with the effectiveness of transfer-dye solutions are discussed.     

Green Luminescent CdTe Quantum Dot Based Fluorescence Nano-Sensor for Sensitive Detection of Arsenic (III)

Arsenic (As³⁺) is a hazardous and ubiquitous element; hence the quantitative detection of arsenic in various kinds of environmental sample is an important issue. Herein, we reported L-cysteine capped CdTe Quantum dot based optical sensor for the fluorometric detection of arsenic (III) in real water sample. The method is based on the fluorescence quenching of QDs with the addition of arsenic solution that caused the reduction in fluorescence intensity due to strong interaction between As³⁺ and L-cysteine to form As(Cys)₃. The calibration curve was linear over 2.0 nM-0.5 μM arsenic with limit of detection (LOD) of 2.0 nM, correlation coefficient (r²) of 0.9698, and relative standard deviation (RSD %) of 5.2%. The Stern-Volmer constant for the quenching of CdTe QDs with As³⁺ at optimized condition was evaluated to be 1.17 × 10⁸ L mol^?1 s^?1. The feasibility of the sensor has been analyzed by checking the inference of common metal ions available in the water such as K⁺, Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Al³⁺, Co²⁺, Cr²⁺, Fe³⁺ and its higher oxidation state As⁵⁺.

Open image in new window

Graphical Abstract Schematic representation of As³⁺ detection by L-Cysteine capped CdTe QDs

     

Supramolecular Polymeric Chemosensor for Biomedical Applications: Design and Synthesis of a Luminescent Zinc Metallopolymer as a Chemosensor for Adenine Detection

Adenine is an important bio-molecule that plays many crucial roles in food safety and biomedical diagnostics. Differentiating adenine from a mixture of adenosine and other nucleic bases (guanine, thymine, cytosine, and uracil) is particularly important for both biological and clinical applications. A neutral Zn^II metallosupramolecular polymer based on acyl hydrazone derived coordination centres (P1) were generated through self-assembly polymerization. It is a linear coordination polymer that behaves like self-standing film. The synthesis, ¹H-NMR characterization, and spectroscopic properties of this supramolecular material are reported. P1 was found to be a chemosensor specific to adenine, with a luminescent enhancement. The binding properties of P1 with common nucleic bases and nucleosides reveal that this supramolecular polymer is very selective to adenine molecules (~20 to 420 times more selectivity than other nucleic bases). The formation constant (K) of P1 to adenine was found to be log K?=?4.10?±?0.02. This polymeric chemosensor produces a specific response to adenine down to 90?ppb. Spectrofluorimetric and ¹H-NMR titration studies showed that the P1 polymer allows each Zn^II coordination centre to bind to two adenine molecules through hydrogen bonding with their imine and hydrazone protons.     

Luminescent compositions for creation of low-voltage cathode luminophores

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 5, pp. 855–857, November, 1991.     

铝合金焊前激光清洗的等离子体光谱在线检测

铝合金焊接技术在工业生产、制造和维修等领域有广泛的应用,焊缝内存在气孔导致焊接质量降低是铝合金焊接技术的常见问题。由于铝合金表面金属氧化物是导致气孔生成的主要来源,对激光清洗过程进行在线检测,不但可以实时分析表面氧化物的清洗状态,而且可以避免基体表面因为过度清洗造成损伤或二次氧化。提出采用激光诱导等离子体光谱(LIBS)在线检测铝合金焊前激光清洗过程,表征清洗后铝合金基体的表面状态。LIBS技术可以对多元素成分同时检测,拥有较低的检出限和较高的准确性。搭建基于Andor Mechelle 5000光谱仪的铝合金焊前激光清洗在线检测系统,剔除空气环境对实验结果的影响,测试6061铝合金表面氧化物和铝合金基体的LIBS光谱,分析两者独特的元素特征谱线,采用X射线能谱(EDS)测试结果验证元素特征谱线的准确性,并探讨激光清洗过程LIBS技术在线检测的可行性。实验测试等离子体光谱谱线强度与激光能量密度之间的关系,获得单次脉冲激光去除铝合金表面氧化物的损伤阈值,结合X射线能谱的检测结果研究激光损伤阈值的成因及影响。研究激光清洗过程等离子体光谱特征谱线与脉冲次数之间的关系,提出基于O/Al特征谱线强度比值作为在线检测清洗效果及二次氧化损伤的评判依据。为验证该评判依据的准确性,将O/Al特征谱线强度比值随清洗次数的变化趋势与X射线能谱测试获得的氧元素原子百分比变化趋势进行对比。实验结果表明:采用200~700 nm范围内激光诱导等离子体谱线特征分析激光清洗状态,可以剔除空气环境的影响;氧元素和铝元素特征谱线准确反映出表面氧化膜与铝合金基体的成分差异;X射线能谱检测元素成分和含量表明氧元素含量随着激光清洗能量密度先减后增,单次清洗铝合金的二次氧化损伤的激光能量阈值为11.46 J·cm-2,小于损伤阈值的激光能量密度对铝合金基体的多次清洗未造成损伤,等离子体光谱特征谱线强度与表面清洗状态相关, 656.5 nm(OⅡ)/396.2 nm(AlⅠ)谱线强度比值≤1.5%为激光清洗干净的依据。研究结果有利于铝合金的激光清洗实时控制技术和焊接装置集成化。     

Design and Synthesis of a Ruthenium(II) Complex-Based Luminescent Probe for Highly Selective and Sensitive Luminescence Detection of Nitric Oxide

Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique Ru^II complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)₃][PF₆]₂, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)₃]²⁺ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)₃]²⁺ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)₃]²⁺ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.     

Novel Fluorometric Turn On Detection of Aluminum by Chalcone-Based Chemosensor in Aqueous Phase

A novel, 100% water-soluble chalcone based chemosensing receptor {1-[3-(2-Hydroxy-phenyl)-3-oxo-propenyl]-naphthalen-2-yloxy}-acetic acid, L was synthesized and characterized. The receptor L is designed based on the chelation enhanced fluorescence (CHEF) mechanism. The chemosensing properties of L were evaluated by UV–vis and fluorescence spectrometric methods. It exhibits highly selective recognition ability towards aluminum ions in water over other metal ions. The binding stoichiometry of L? Al³⁺ complex is 2:1 by means of Job’s plot and the detection limit is 5.66?×?10^??8 M.     

Luminescent transformers based on activated glasses for lasers with lamp pumping

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 1, pp. 95–99, July, 1991.     

苯胺蓝分光光度法测定痕量铬(Ⅵ)

在HCI介质中,铬(Ⅵ)与过量I-反应生成黄色 I-3,继而与水溶性苯胺蓝阳离子形成离子缔合物,使得苯胺蓝溶液褪色,其在605nm处产生一个强吸收峰.在最佳实验条件下,Cr(Ⅵ)的浓度在4.0×10-7-1.2×10-5mol/L范围内符合比耳定律.表观摩尔吸光系数ε为1.10×106L·Mol-1·cm-1.该法用于分析测定沱江水样中Cr(Ⅵ)的含量,结果令人满意.     

Synthesis of Copper Metal Organic Framework Based on Schiff Base Tricarboxylate Ligand for Highly Selective and Sensitive Detection of 2,4,6-Trinitrophenol in Aqueous Medium

Journal of Fluorescence - By using Schiff base tricarboxylate ligand 5-(4-carboxybenzylideneamino)isophthalic acid (H3CIP), a new imine functionalized copper metal organic framework (MOF) has been...     

Acid Synthesis of Luminescent Amine-functionalized or Erbium-doped Silica Spheres for Biological Applications

In this work we discuss and investigate the morphological and optical properties of luminescent silica spheres which can have interesting applications in bioimaging and biosensing. The spheres are synthesized following an acid route by the hydrolysis and condensation of tetraethylortosilicate (TEOS) and can be functionalized by incorporation of aminopropyl-triethoxysilane (APTES) during the synthesis, inducing a significant luminescence that can be attributed to a recombination mechanism from localized organic defects related to –NH₂ groups. It is shown that the acid synthesis route produces very regular spherical particles, but their diameter vary in the range of 200–4,000 nm. The luminescence properties have been investigated and optimized by variation of the annealing temperature for the functionalized spheres, obtaining the most efficient PL emission after a thermal treatment of 1 h at 600 °C in air. Moreover, the possibility to introduce rare earths like erbium in the spheres was also studied and the corresponding Er³ luminescence emission at 1.53 μm is reported in terms of intensity and lifetime, pointing out that erbium can be easily and efficiently incorporated during the acid synthesis giving high PL intensity with a good lifetime of 3.9 ms.     

狭长CsI(Tl)闪烁体发光效率的研究

提出了基于狭长CsI（Tl）闪烁体和面阵CCD器件,采用光纤和光纤面板进行光耦合及传输,以扇形束线阵扫描方式实现对X射线探测与成像的工业X-CT系统探测器方案.基此,通过物理分析及数学建模,利用Matlab模拟研究了X光能量小于450 keV时狭长CsI（Tl）闪烁体的发光效率等性能指标.研究结果表明：当光电吸收截面μph和康普顿吸收截面μc分别为0.000313和0.0000295、反射层反射系数R和衬底反射系数Rs分别取0.95和0.8、荧光线性吸收系数σ取0.000222 μm－1时,得到狭长CsI(Tl)闪烁晶体的长度l、高度h和宽度w取值范围分别是926～4512 μm、242～5000 μm和242～5000 μm的结论.在此范围内,既可使闪烁晶体有较好的空间分辨率又可获得最高的发光效率.     

Luminescent Properties of Colloidal Ag2S Quantum Dots for Photocatalytic Applications

Physics of the Solid State - The structural and optical properties of colloidal Ag2S quantum dots in different environments are studied. With the help of transmission electron microscopy, X-ray...