Tipikin D S, Earle K A, Freed J H
Cornell University, Department of Chemistry and Chemical Biology, Ithaca, NY, 14853.
Appl Magn Reson. 2010 Jan 1;37(1-4):819-832. doi: 10.1007/s00723-009-0088-1.
The sensitivity of a high frequency electron spin resonance (ESR) spectrometer depends strongly on the structure used to couple the incident millimeter wave to the sample that generates the ESR signal. Subsequent coupling of the ESR signal to the detection arm of the spectrometer is also a crucial consideration for achieving high spectrometer sensitivity. In previous work, we found that a means for continuously varying the coupling was necessary for attaining high sensitivity reliably and reproducibly. We report here on a novel asymmetric mesh structure that achieves continuously variable coupling by rotating the mesh in its own plane about the millimeter wave transmission line optical axis. We quantify the performance of this device with nitroxide spin-label spectra in both a lossy aqueous solution and a low loss solid state system. These two systems have very different coupling requirements and are representative of the range of coupling achievable with this technique. Lossy systems in particular are a demanding test of the achievable sensitivity and allow us to assess the suitability of this approach for applying high frequency ESR to the study of biological systems at physiological conditions, for example. The variable coupling technique reported on here allows us to readily achieve a factor of ca. 7 improvement in signal to noise at 170 GHz and a factor of ca. 5 at 95 GHz over what has previously been reported for lossy samples.
高频电子自旋共振(ESR)光谱仪的灵敏度在很大程度上取决于用于将入射毫米波耦合到产生ESR信号的样品的结构。ESR信号随后耦合到光谱仪的检测臂也是实现高光谱仪灵敏度的关键考虑因素。在之前的工作中,我们发现为了可靠且可重复地实现高灵敏度,需要一种连续改变耦合的方法。我们在此报告一种新颖的不对称网状结构,该结构通过在其自身平面内围绕毫米波传输线光轴旋转网状物来实现连续可变耦合。我们用氮氧化物自旋标记光谱在有损水溶液和低损耗固态系统中对该装置的性能进行了量化。这两个系统具有非常不同的耦合要求,并且代表了用该技术可实现的耦合范围。特别是有损系统对可实现的灵敏度是一个严格的测试,例如使我们能够评估这种方法是否适合在生理条件下将高频ESR应用于生物系统的研究。这里报道的可变耦合技术使我们能够轻松实现约7倍的信号噪声比提升(在170 GHz时)和约5倍的提升(在95 GHz时),相比之前报道的有损样品的情况。