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Absolute measurements of fluorescence polarization at high pressures

机译:高压下荧光偏振的绝对测量

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The measurement of polarization of the fluorescence of solutions under high pressure is rendered uncertain by the photoelastic birefringency of the windows, and needs a correction dependent upon the fraction of the light emerging from a window with polarization normal to that of the incident light (scrambling coefficient). This correction, which increases rapidly with applied pressure, differs according to whether the method of measurement employs rotation of the excitation polarizer (T format) or the emission polarizer (L format), and the latter is shown to involve the more reliable and the smaller correction. A four window pressure bomb housing a 1 ml volume cuvette that permits absorption and fluorescence measurements up to 4 kbar is described. The polarization correction up to 2.5 kbar was determined. Its reliability was demonstrated by measurements of the fluorescence polarization spectra of fluorophores in solvents of high viscosity at all pressures and by comparison of isopiestic and isothermal measurements of a fluorophore in isobutanol, a fluid solvent with viscosity that changes rapidly with pressure or temperature.
机译:窗口的光弹性双折射使得不确定溶液在高压下的荧光偏振度变得不确定,并且需要进行校正,具体取决于从窗口射出的光的偏振度与入射光的偏振态垂直的比例(扰乱系数) )。随施加压力而迅速增加的该校正因测量方法是采用激发偏振片(T格式)还是发射偏振片(L格式)的旋转而有所不同,并且显示后者涉及更可靠和更小更正。描述了一种装有1毫升容积比色皿的四窗口压力弹,该比色皿允许进行高达4 kbar的吸收和荧光测量。确定了高达2.5 kbar的极化校正。通过在所有压力下测量高粘度溶剂中荧光团的荧光偏振光谱,并通过比较异丁醇中荧光团的等密度和等温测量值来证明其可靠性,异丁醇是一种粘度随压力或温度而迅速变化的流体溶剂。

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