On the behaviour of Eu oxo-species in molten NaBr–NaI (0.77:0.23) mixture at 973 K

The interaction of Eu₂O₃ with molten NaBr–NaI (0.77:0.23) mixture at 973 K was studied by sequential addition method with the use of YSZ membrane oxygen electrode for controlling of course of the process. The Red-Ox process is accompanied with formation of EuO in the melt. The total solubility of EuO (sum of concentration of Eu²⁺, O^2–, non-dissociated EuO) in the molten NaBr–NaI at 973 K (mole fraction 2.7 × 10^–4) is considerably lower than in pure NaI melt (4.2 × 10^–4), which can be explained using the ‘hole’ model by reduction of a number of holes of comparable with EuO particle size because of addition of smaller bromide ion to the iodide melt.

The solubility of EuO is appreciably affected by its dispersity and the value of surface energy causing these solubility changes is estimated as 37 J m^–2.     

新型双β-二酮、邻菲罗啉和铕(Ⅲ)三元配合物的合成与发光

合成了一个新型双β-二酮有机配体1,3-双[3-(2-噻吩基)-3-氧代丙酰基]苯、邻菲罗啉和铕的三元配合物,并应用红外光谱、紫外-可见光谱、元素分析和热重-差热分析等对配合物进行了组成确定和结构表征.荧光分析结果表明,配合物612 nm处的发射光谱为中心离子Eu3+的特征红光,属5D0→7F2跃迁带,峰形尖锐,单色性...     

吡啶—2,6—二羧酸体系导数荧光法同时测定铀,钐,铕,铽,镝

本研究了吡啶－２，６－二羧酸（ＤＰＡ）体系导数荧光法同时测定铀，钐，铕，铽，镝的最佳条件。在ｐＨ５．５，４．８×１０＾－＾５ｍｏｌ／ＬＤＰＡ，激发波长２７２ｎｍ的条件下，可分别在５１８，６３９，６２１，５３９和６６ｎｍ处测定铀，钐，铕，铽和镝，检测限分别达到７，０．４，０．００４，０．０２６和０．２５ｎｇ／ｍＬ。应用本法测定了混合成试液中上术五种离子含量，回收率为９２．３－１０８．１％。     

Investigation of odd-parity Rydberg states of Eu I with autoionization detection

Isolated-core-excitation (ICE) scheme and autoionization detection are employed to study the bound Rydberg states of europium atom. The high-lying states with odd parity have been measured using the autoionization detection method with three different excitation paths via 4f⁷6s6p[ ⁸P_5/2], 4f⁷6s6p[ ⁸P_7/2] and 4f⁷6s6p[ ⁸P_9/2] intermediate states, respectively. In this paper the spectra of bound Rydberg states of Eu atom are reported, which cover the energy regions from 36000~cm^-1 to 38250~cm^-1 and from 38900~cm^-1 to 39500 cm^-1. The study provides the information about level energy, the possible J values and relative line intensity as well as the effective principal quantum number n^* for these states. This work not only confirms the previous results of many states, but also discovers 11 new Rydberg states of Eu atom.     

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Coumarin‐sensitized, long‐wavelength‐absorbing luminescent Eu^III‐complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen‐based chelating framework that is attached through a short linker to a 7‐hydroxycoumarin, a 7‐B(OH)₂‐coumarin, a 7‐O‐(4‐pinacolatoboronbenzyl)‐coumarin or a 7‐O‐(4‐methoxybenzyl)‐coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high‐yielding steps. The sensitivity of coumarin photophysics to the 7‐substituent enables modulation of the antenna‐absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate‐based functionalities (cages) with H₂O₂ yielded the corresponding 7‐hydroxycoumarin species. The same species was produced with peroxynitrite in a ×10⁶–10⁷‐fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu‐complex was quenched by ONOO^?. We have shown that preliminary screening of simple coumarin‐based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in Eu^III‐excitation profile in the fully elaborated complex. Taken together, our results show that the 7‐hydroxycoumarin antenna is a viable scaffold for the construction of turn‐on and ratiometric luminescent probes.     

Synthesis of Eu(III) and Tb(III) Complexes with Two New Amide Type Podands and Their Luminescence Properties

ＩｎｔｒｏｄｕｃｔｉｏｎＬａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎｂｅｃａｕｓｅｏｆｔｈｅｉｒｉｍｐｏｒｔａｎｔａｐｐｌｉｃａｔｉｏｎｓ .1ＩｎｐａｒｔｉｃｕｌａｒＥｕ(ＩＩＩ)ａｎｄＴｂ(ＩＩＩ)ｃａｎｂｅｃｈａｒａｃｔｅｒｉｚｅｄｂｙｌｏｎｇ ｌｉｖｅｄ(ｍｓｔｉｍｅｓｃａｌｅ)ａｎｄｓｔｒｏｎｇｌｕｍｉｎｅｓｃｅｎｔｅｌｅｃｔｒｏｎｉｃａｌｌｙｅｘ ｃｉｔｅｄｓｔａｔｅｓ ,ｗｈｉｃｈｍａｋｅｓｔｈｅｍｉｍｐｏｒｔａｎｔｉｎａｎａｌｙｔｉｃａｌｃｈｅｍ…     

Ni[S2 P(OCH2 CH2 Ph)2]2·2Py的制备及结构表征

O,O’-二烃基二硫代磷酸根及其过渡金属配合物能阻止烃类自动氧化,广泛地用作润滑油的抗氧剂、燃油的添加剂、高分子材料的稳定剂和人造橡胶的硫化促进剂;在生物学上具有杀虫、抗菌、抗癌和抑制酶水解等特性[1-3]。[(RO)2PS2]nM用作润滑油抗氧剂时,为了有效地缩减氧化作用,一般     

Observation of resonance electronic and non‐resonance‐enhanced vibrational natural Raman optical activity

Natural resonance electronic Raman optical activity (ROA) is observed for the first time. Coincidently, the first example of vibrational ROA enhanced by low‐lying electronic transition is reported. These new phenomena were measured using the rare‐earth complex Eu(tfc)₃ (+)‐tris[3‐trifluoroacetyl‐D ‐camphorato]europium(III), where electronic resonance occurs between the 532‐nm laser excitation and the ⁷F₁ → ⁵D₁ transition of the Eu³⁺ metal center. Electronic Raman spectra involve the Raman transitions terminating on the low‐lying electronic states of Eu(tfc)₃. The observed vibrational ROA spectra are enhanced relative to typical ROA spectra by the proximity of vibrational states of Eu(tfc)₃ to its low‐lying electronic states with significant magnetic‐dipole character, whereas the parent vibrational Raman spectra do not appear to be resonance‐enhanced since the 532‐nm vibrational Raman spectrum has similar relative intensities to the corresponding Raman spectrum measured with 1064‐nm laser excitation. Copyright © 2010 John Wiley & Sons, Ltd.     

Oxidative Conversion of a Europium(II)‐Based T1 Agent into a Europium(III)‐Based paraCEST Agent that can be Detected In Vivo by Magnetic Resonance Imaging

The Eu^II complex of 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) tetra(glycinate) has a higher reduction potential than most Eu^II chelates reported to date. The reduced Eu^II form acts as an efficient water proton T₁ relaxation reagent, while the Eu^III form acts as a water‐based chemical exchange saturation transfer (CEST) agent. The complex has extremely fast water exchange rate. Oxidation to the corresponding Eu^III complex yields a well‐defined signal from the paraCEST agent. The time course of oxidation was studied in vitro and in vivo by T₁‐weighted and CEST imaging.