Abstract

This article reports details of a new setup including an optical flow cell and devices which can increase pressure up to 400MPa by controlling the ramp rate. It is composed of two high pressure syringe pumps which can make liquids flowing up to 4cm3/mn. The optical flow cell can contains aqueous solutions and allow carry out pulse radiolysis experiments with a pulsed 10-MeV electron beam by performing in situ and time resolved optical analysis, such as transient UV–visible absorption or fluorescence spectroscopy. A Labview-program has been developed to drive and monitor automatons which regulate pressure, make solution flow under pressure, carry out operations such as filling, emptying or cleaning the system under safe conditions. Two results are exhibited: 1/associated to phosphate buffer, the fluorescence spectrum of the fluorescein pH-sensor has been performed under pressure. Phosphate pKa is confirmed to be very sensitive to pressure increase even up to 300MPa. 2/a time-resolved absorption spectroscopy of hydrated electron in deaerated water has been conducted up to 350MPa with a continuous flow of sample. In presence of tertio-butanol and bisTris pH7-buffer in solution, the spectral shift of hydrated electron is finely reproduced. BisTris is also confirmed as insensitive buffer under high pressure and its reduction by hydrated electron remains constant with a rate constant of (4.6±0.6)×108M−1s−1.

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