National Biomedical EPR Center, Department of Biophysics, Medical College of Wisconsin, 8701 Watertown Plank Road, Milwaukee, WI 53226, USA.
J Magn Reson. 2011 Aug;211(2):228-33. doi: 10.1016/j.jmr.2011.06.004. Epub 2011 Jun 13.
A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented.
连续波 (CW) 电子顺磁共振 (EPR) 谱通常显示为应用 100 kHz 磁场调制的一阶谐波响应,这用于通过降低 1/f 噪声水平来提高灵敏度。然而,任何幅度的磁场调制都会导致光谱展宽,并使 EPR 光谱强度至少降低两倍。在本文中,开发了一种避免这些折衷并提供避免 1/f 噪声的方法的 CW 快速扫描光谱技术。该技术称为非绝热快速扫描 (NARS) EPR,它包括以小线圈以足够高的重复率线性地重复扫过光谱片段中的极化磁场,以使接收器噪声、微波相位噪声和环境微震,每种噪声都具有 1/f 特性,得以克服。然而,扫描速度足够慢,以至于避免了绝热响应,并且自旋系统始终接近热平衡。从光谱片段中重复获取的光谱进行平均。在这些条件下,获得了没有展宽或信号强度损失的无失真纯吸收光谱。应用数字滤波器(例如移动平均滤波器)来去除高频噪声,该噪声的带宽与在传统的锁定检测场调制中使用积分时间常数相当。给出了 L 波段和 X 波段的氮氧自由基光谱。