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Monitoring inorganic pyrophosphatase activity with the fluorescent dizinc(ii) complex of a macrocycle bearing one dansylamidoethyl antenna.
Dalton Transactions ( IF 4 ) Pub Date : 2020-06-16 , DOI: 10.1039/d0dt01673j
Ana Cruz 1 , Ara Núñez-Montenegro , Pedro Mateus , Rita Delgado
Affiliation  

The dizinc(II) complexes of L were used for the recognition of anions by fluorescence spectroscopy (L is a heteroditopic hexaazamacrocycle with two diethylenetriamine coordination heads with 2-methylpyridyl and dansylamido ethyl arms, and m-xylyl spacers). The protonation of L and stability constants of its zinc(II) complexes were determined in aqueous solution, at 298.2 ± 0.1 K and I = 0.10 ± 0.01 M in KNO3. At a 2 : 1 Zn2+/L ratio, the dinuclear complexes clearly dominate. The ligand alone does not display fluorescence changes upon increasing the pH value, but in the presence of Zn2+ the emission reaches a maximum at pH ≅ 7.5, at which 95% of the ligand is in the dinuclear complex form. The emission appears concomitantly with the [Zn2H−1L]3+ species formation, which supports that the latter complex corresponds to the metal-promoted deprotonation of dansylamide NH. The [Zn2H−1L]3+ complexes were used for the recognition of phosphate and polyphosphate anions in aqueous solution buffered at pH 7.5 with 2 mM PIPPS, at 298.2 K. The binding of anions causes a decrease of the emission. The association constant determination revealed that HPPi3− is the strongest bound anion (log Kapp = 5.57), followed by HATP3− (two times weaker), and the remaining anions show lower binding constants, with HPO42− having the weakest uptake by the receptor. The observed selectivity of the [Zn2H−1L]3+ receptor for PPi in relation to HPO42−, and the fact that the formation of the [Zn2H−1L]3+ complex is not disturbed by the presence of Mg2+, allowed monitoring of the PPi hydrolysis by using inorganic pyrophosphatase in real-time.

中文翻译:

使用带有一个dansylamidoethyl天线的大环的荧光dizinc(ii)配合物监测无机焦磷酸酶活性。

所述dizinc(II)配合物的大号被用于通过荧光光谱法识别阴离子(大号是heteroditopic hexaazamacrocycle与2-甲基吡啶基二乙烯三胺2协调头和dansylamido乙基臂,和-二甲苯间隔物)。在水溶液中测定了L的质子化及其锌(II)配合物的稳定常数,在KNO 3中为298.2±0.1 K和I = 0.10±0.01M 。在2:1 Zn 2+ / L在比例上,双核复合物显然占主导地位。单独的配体不会随pH值的增加而显示荧光变化,但是在Zn 2+的存在下,发射在pH≥7.5时达到最大值,此时95%的配体为双核络合物形式。发射与[Zn 2 H -1 L ] 3+物种形成同时出现,这表明后者的络合物​​对应于金属促进的丹磺酰胺NH的去质子化。[Zn 2 H -1 L ] 3+络合物用于识别在pH 7.5和2mM PIPPS缓冲于298.2 K的水溶液中的磷酸根和多磷酸根阴离子。阴离子的结合导致发射减少。缔合常数测定表明,HPPi 3-是最强的结合阴离子(log  K app = 5.57),其次是HATP 3-(弱两倍),其余阴离子显示出较低的结合常数,其中HPO 4 2-具有最弱的结合常数。被受体摄取。观察到的[Zn 2 H -1 L ] 3+受体对PPi的相对于HPO 4 2-的选择性,以及形成[Zn ]的事实Mg 2+的存在不会干扰2 H -1 L ] 3+络合物,可以通过使用无机焦磷酸酶实时监控PPi水解。
更新日期:2020-07-17
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