Price W D, Schnier P D, Jockusch R A, Strittmatter E F, Williams E R
Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Am Chem Soc. 1996 Oct 30;118(43):10640-4. doi: 10.1021/ja961812r.
Molecular activation by blackbody photons, first postulated in 1919 by Perrin, plays a dominant role in the unimolecular dissociation of large ions trapped at low pressure in a Fourier-transform mass spectrometer. Under readily achievable experimental conditions, molecular ions of the protein ubiquitin equilibrate with the blackbody radiation field inside the vacuum chamber. The internal energy of a population of these ions is given by a Boltzmann distribution. From the temperature dependence of unimolecular dissociation rate constants measured in the zero-pressure limit, Arrhenius activation parameters equal to those in the high-pressure limit are obtained.
黑体光子引起的分子活化，由佩兰于1919年首次提出，在傅里叶变换质谱仪中低压捕获的大离子的单分子解离中起主导作用。在易于实现的实验条件下，蛋白质泛素的分子离子与真空室内的黑体辐射场达到平衡。这些离子群体的内能由玻尔兹曼分布给出。从零压力极限下测量的单分子解离速率常数的温度依赖性，可得到与高压极限下相等的阿伦尼乌斯活化参数。
