Tseitlin Mark, Yu Zhelin, Quine Richard W, Rinard George A, Eaton Sandra S, Eaton Gareth R
Department of Chemistry and Biochemistry, University of Denver, Denver, CO 80210, USA.
School of Engineering and Computer Science, University of Denver, Denver, CO 80210, USA.
J Magn Reson. 2014 Dec;249:126-134. doi: 10.1016/j.jmr.2014.10.011. Epub 2014 Oct 30.
The use of multiple synchronized outputs from an arbitrary waveform generator (AWG) provides the opportunity to perform EPR experiments differently than by conventional EPR. We report a method for reconstructing the quadrature EPR spectrum from periodic signals that are generated with sinusoidal magnetic field modulation such as continuous wave (CW), multiharmonic, or rapid scan experiments. The signal is down-converted to an intermediate frequency (IF) that is less than the field scan or field modulation frequency and then digitized in a single channel. This method permits use of a high-pass analog filter before digitization to remove the strong non-EPR signal at the IF, that might otherwise overwhelm the digitizer. The IF is the difference between two synchronized X-band outputs from a Tektronix AWG 70002A, one of which is for excitation and the other is the reference for down-conversion. To permit signal averaging, timing was selected to give an exact integer number of full cycles for each frequency. In the experiments reported here the IF was 5kHz and the scan frequency was 40kHz. To produce sinusoidal rapid scans with a scan frequency eight times IF, a third synchronized output generated a square wave that was converted to a sine wave. The timing of the data acquisition with a Bruker SpecJet II was synchronized by an external clock signal from the AWG. The baseband quadrature signal in the frequency domain was reconstructed. This approach has the advantages that (i) the non-EPR response at the carrier frequency is eliminated, (ii) both real and imaginary EPR signals are reconstructed from a single physical channel to produce an ideal quadrature signal, and (iii) signal bandwidth does not increase relative to baseband detection. Spectra were obtained by deconvolution of the reconstructed signals for solid BDPA (1,3-bisdiphenylene-2-phenylallyl) in air, 0.2mM trityl OX63 in water, N perdeuterated tempone, and a nitroxide with a 0.5G partially-resolved proton hyperfine splitting.
使用任意波形发生器(AWG)的多个同步输出提供了以不同于传统电子顺磁共振(EPR)的方式进行EPR实验的机会。我们报告了一种从通过正弦磁场调制产生的周期性信号重建正交EPR谱的方法,例如连续波(CW)、多谐波或快速扫描实验。信号被下变频到一个低于场扫描或场调制频率的中频(IF),然后在单个通道中数字化。这种方法允许在数字化之前使用高通模拟滤波器来去除中频处的强非EPR信号,否则该信号可能会使数字化仪过载。中频是泰克AWG 70002A的两个同步X波段输出之间的差值,其中一个用于激发,另一个用于下变频参考。为了允许信号平均,选择定时以给出每个频率的完整周期的确切整数。在本文报道的实验中,中频为5kHz,扫描频率为40kHz。为了产生扫描频率为中频八倍的正弦快速扫描,第三个同步输出产生一个方波,该方波被转换为正弦波。使用布鲁克SpecJet II进行数据采集的定时由来自AWG的外部时钟信号同步。在频域中重建基带正交信号。这种方法具有以下优点:(i)消除了载波频率处的非EPR响应,(ii)从单个物理通道重建实部和虚部EPR信号以产生理想的正交信号,以及(iii)相对于基带检测,信号带宽不会增加。通过对空气中固体BDPA(1,3 - 双亚苯基 - 2 - 苯基烯丙基)、水中0.2mM三苯甲基OX63、N - 全氘代TEMPONE以及具有0.5G部分分辨质子超精细分裂的氮氧化物的重建信号进行去卷积获得光谱。