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比较 4f-4f 跃迁的吸收光谱法,以探索尿嘧啶与 Nd(III)和 Zn(II)同时配位的动力学及其相关热力学。

Comparative absorption spectroscopy involving 4f-4f transitions to explore the kinetics of simultaneous coordination of uracil with Nd(III) and Zn(II) and its associated thermodynamics.

机构信息

Department of Chemistry, Manipur University, Canchipur-795003, Imphal, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2011 Oct 15;81(1):296-303. doi: 10.1016/j.saa.2011.06.013. Epub 2011 Jun 22.

DOI:10.1016/j.saa.2011.06.013
PMID:21752705
Abstract

The interaction of uracil with Nd(III) has been explored in presence and absence of Zn(II) using the comparative absorption spectroscopy involving the 4f-4f transitions in different solvents. The complexation of uracil with Nd(III) is indicated by the change in intensity of 4f-4f bands expressing in terms of significant change in oscillator strength and Judd-Ofelt parameters. Intensification of this bands became more prominent in presence of Zn(II) suggesting the stimulative effect of Zn(II) towards the complexation of Nd(III) with uracil. Other spectral parameters namely Slator-Condon (F(k)'s), nephelauxetic effect (β), bonding (b(1/2)) and percent covalency (δ) parameters are computed to correlate their simultaneous binding of metal ions with uracil. The sensitivities of the observed 4f-4f transitions towards the minor coordination changes around Nd(III) has been used to monitor the simultaneous coordination of uracil with Nd(III) and Zn(II). The variation of intensities (oscillator strengths and Judd-Ofelt parameters) of 4f-4f bands during the complexation has helped in following the heterobimetallic complexation of uracil. Rate of complexation with respect to hypersensitive transition was evaluated. Energy of activation and thermodynamic parameters for the complexation reaction were also determined.

摘要

采用比较吸收光谱法,研究了在存在和不存在 Zn(II) 的情况下,尿嘧啶与 Nd(III) 的相互作用,该方法涉及不同溶剂中的 4f-4f 跃迁。尿嘧啶与 Nd(III) 的络合作用通过 4f-4f 带的强度变化来表示,这表现在振子强度和 Judd-Ofelt 参数的显著变化。在存在 Zn(II) 的情况下,这些带的强度增强更为明显,这表明 Zn(II)对 Nd(III)与尿嘧啶的络合具有促进作用。其他光谱参数,如 Slator-Condon(F(k)'s)、离域效应(β)、键合(b(1/2))和共价度(δ)参数,用于计算它们与金属离子同时与尿嘧啶结合的相关性。观察到的 4f-4f 跃迁对 Nd(III)周围微小配位变化的敏感性被用于监测尿嘧啶与 Nd(III)和 Zn(II)的同时配位。4f-4f 带的强度(振子强度和 Judd-Ofelt 参数)在络合过程中的变化有助于跟踪尿嘧啶的杂双金属络合。评估了相对于高敏感跃迁的络合速率。还确定了配合反应的活化能和热力学参数。

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