Dual-function pH and oxygen phosphonated trityl probe.

Dual-function pH and oxygen phosphonated trityl probe.
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双功能pH和氧磷酸trityl探针。

DOI:
10.1021/ac3008994
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发表时间:
2012-07-17
影响因子:
7.4
通讯作者:
Khramtsov, Valery V.
Khramtsov, Valery V.
中科院分区:
化学1区
文献类型:
--
作者:
Bobko, Andrey A.;Dhimitruka, Ilirian;Komarov, Denis A.;Khramtsov, Valery V.

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三芳基甲基自由基(TAMs)用作EPR光谱和成像应用的持久顺磁探针,以及MRI和质子-电子双共振成像(PEDRI)的超极化和造影剂。最近,我们提出了双功能pH和氧TAM探针的概念,其基于将可电离基团并入TAM结构中(J. Am. 2007,129,7240-7241)。本文报道了三苯甲基膦酸酯氘代衍生物pTAM的合成。TAM结构中膦酰基取代基的存在使其EPR光谱在pH 6 - 8的生理范围内具有pH敏感性,磷的超精细分裂是方便且高度敏感的pH标记物(光谱灵敏度,3ΔaP/ΔpH = 0.5 G/pH单位; pH测量的准确度,±0.05)。此外,用氘核取代36个甲基质子,使pTAM的单个线宽显著降低至40 mG,因此,提供了对pO 2线宽加宽的高灵敏度(ΔH/Δ pO 2 <0.4 mG/mmHg; pO 2测量的准确度<1 mmHg)。pH和[O2]对pTAM EPR谱的影响的独立特征为该探针提供了双重功能,允许从单个EPR谱提取两个参数。
Triarylmethyl radicals, TAMs, are used as persistent paramagnetic probes for EPR spectroscopic and imaging applications and as hyperpolarizing and contrast agents for MRI and proton-electron double-resonance imaging, PEDRI. Recently we proposed the concept of dual function pH and oxygen TAM probes based on the incorporation of ionizable groups into the TAM structure (J. Am. Chem. Soc. 2007, 129, 7240–7241). In this paper we report the synthesis of deuterated derivative of phosphonated trityl radical, pTAM. The presence of phosphono substitutes in the structure of TAM provides pH sensitivity of its EPR spectrum in the physiological range of pH from 6 to 8, the phosphorus hyperfine splitting being convenient and highly sensitive pH marker (spectral sensitivity, 3ΔaP/ΔpH≈0.5 G/pH unit; accuracy of pH measurements, ±0.05). In addition, substitution of 36 methyl protons with deuterons significantly decreased the individual linewidth of pTAM down to 40 mG and, as consequence, provided high sensitivity of the linewidth broadening to pO2 (ΔH/ΔpO2≈0.4 mG/mmHg; accuracy of pO2 measurements, ≈1 mmHg). The independent character of pH and [O2] effects on the EPR spectra of pTAM provides dual functionality to this probe allowing for an extraction of both parameters from a single EPR spectrum.
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