Preparation and EPR studies of lithium phthalocyanine radical as an oxymetric probe

被引:43
作者
Afeworki, M [1 ]
Miller, NR [1 ]
Devasahayam, N [1 ]
Cook, J [1 ]
Mitchell, JB [1 ]
Subramanian, S [1 ]
Krishna, MC [1 ]
机构
[1] NCI, Radiat Biol Branch, Div Clin Sci, NIH, Bethesda, MD 20892 USA
关键词
lithium phthalocyanine; oxymetry; FT EPR; RF EPR; free radical;
D O I
10.1016/S0891-5849(98)00039-2
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The electron paramagnetic resonance (EPR) spectrum of the paramagnetic center in solid lithium phthalocyanine, LiPc, exhibits a pO(2) (partial pressure of oxygen)-dependent line width. The compound is insoluble in water and is not easily biodegradable and, therefore, is a useful spin probe for quantitative in vivo oxymetry. Because EPR spectrometry is potentially a useful technique to quantitatively obtain in vivo tissue pO(2), such probes can be used to obtain physiological information. In this paper, a simple experimental procedure for the preparation of LiPc using potentiostatic electrochemical methods is described. The setup was relatively inexpensive and easy to implement. A constant potential ranging from 0.05 to 0.75 V versus Ag+/AgCl(s) was used for obtaining LiPc. The EPR spectral studies were carried out using spectrometers operating at X-band and at radiofrequency (RF) at different pO(2) values to characterize the spectral response of these crystals. The results indicate that, depending on the electrolysis conditions, the products contain mixtures of crystals exhibiting pO(2)-sensitive and pO(2)-insensitive line widths, Electrolysis conditions are reported whereby the pO(2)-sensitive LiPc crystals were the predominant product. The influence of the working surface of the electrode and the electrolysis time on the yield were also evaluated. The crystals of LiPc were also studied using a time-domain RF EPR spectrometer. In time-domain EPR, the signals that survive beyond the spectrometer dead time are mainly the narrow lines corresponding to the pO(2)-sensitive crystals, whereas the signals arising from the pO(2)-insensitive component of LiPc were found not to survive beyond the spectrometer dead time. This signal survival makes the time-domain EPR method more sensitive for pO(2) measurements using LiPc because the line width becomes very narrow at very low pO(2) and, concomitantly, the relaxation time T-2 longer, with no modulation or power saturation artifacts that are encountered as in the continuous wave (cw) mode. Further, minimal contributions from object motion in the spectral data obtained using time-domain methods make it an advantage for in vivo applications. Published by Elsevier Science Inc.
引用
收藏
页码:72 / 78
页数:7
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