Ultrafast Chemistry of Water Radical Cation, H2O•+, in Aqueous Solutions.

Oxidation reactions by radicals constitute a very important class of chemical reactions in solution. Radiation Chemistry methods allow producing, in a controlled way, very reactive oxidizing radicals, such as OH•, CO3•-, NO3•, SO4•-, and N3•. Although the radical cation of water, H2O•+, with a very short lifetime (shorter than 1 ps) is the precursor of these radicals in aqueous solutions, its chemistry is usually known to be limited to the reaction of proton transfer by forming OH• radical. Herein, we stress situations where H2O•+ undergoes electron transfer reaction in competition with proton transfer.

Pulse Radiolysis Using Very-high-energy Ions for Optimizing Cancer Therapy.

Cancer therapy by means of high-energy ions is very efficient. As a consequence of the linear-energy-transfer effect only a negligible part of the produced free radicals can escape combination processes to form molecular products and to cause undesired side processes. Positrons (e⁺) and γ-rays, generated by the nuclear interaction of high-energy ions in the medium, serve in monitoring the radiation dose absorbed by the tumor. However, due to the dipole nature of water molecules a small proportion of thermalized positrons (e⁺th) can become solvated (e⁺aq). Hence, they are stabilized, live longer and can initiate side reactions. In addition, positronium (Ps), besides solvated electrons (e⁺aq), can be generated and involved in the reaction mechanisms. For a better understanding of the reaction mechanisms involved and to improve cancer therapy, a time-resolved pulse radiolysis instrument using high-energy particles is discussed here. The proposed method is examined and recommended by CERN experts. It is planned to be realized at the MedAustron Radiation Therapy and Research Centre in Wiener Neustadt, Austria.

Implementation of laser induced fluorescence in a pulse radiolysis experiment--a new way to analyze resazurin-like reduction mechanisms.

Resazurin (RNO) reduction by hydrated electrons produces a fluorescent molecule: resorufin (RN). To take advantage of RN fluorescence, a novel setup is designed by implementing fluorescence detection induced by laser in a pulse radiolysis experiment. Time resolved fluorescence spectra were recorded with a fast gated intensified CCD camera during the reduction of RNO from µs to ms. Two 532 nm laser types have been used to describe the short µs range by a 5 ns Q-switch laser and the µs-ms range by a CW DPSS laser. By fitting the simulated model to the experimental data a second order rate constant of 10(9) M(-1) s(-1) was re-evaluated. This method should be considered in the near future in many in situ and real time measurements for evaluating radical production.

Development of double-decker pulse radiolysis.

Double-decker pulse radiolysis (DDPR), which utilizes double-decker electron beams, was investigated to develop a new pulse radiolysis with a high time resolution. The double-decker electron beams were generated by injecting two UV pulses into a photocathode radio-frequency gun. In the pulse radiolysis, one electron beam was used as a pump beam, and the other was converted to a probe pulse. Finally, as its first application, the DDPR was successfully used for observing solvated electrons in water, with a 10%-90% rise time of 8.6 ps.

Installation and testing of a focusing mirror at beamline X28C for high flux x-ray radiolysis of biological macromolecules.

The NSLS X28C white-light beamline has been upgraded with a focusing mirror in order to provide increased x-ray density and a wide selection of beam shapes at the sample position. The cylindrical single crystal silicon mirror uses an Indalloy 51 liquid support bath as both a mechanism for heat transfer and a buoyant support to counter the effects of gravity and correct for minor parabolic slope errors. Calorimetric measurements were performed to verify that the calculated more than 200-fold increase in flux density is delivered by the mirror at the smallest beam spot. The properties of the focused beam relevant to radiolytic footprinting, namely, the physical dimensions of the beam, the effective hydroxyl radical dose delivered to the sample, and sample heating upon irradiation, have been studied at several mirror angles.

Effect of pressure on pulse radiolysis reduction of proteins.

Pulse radiolysis experiments were performed on proteins under pressure. Whereas many spectroscopic techniques have shown protein modifications at different pressure ranges, the present measurements performed using the water radiolysis allowed to generate radical species and to study the mechanisms implied in their reactions with proteins. This work gives the first results obtained on the effects of pressure on the rate constants of the proteins reduction by the hydrated electron at pressures up to 100 MPa. The reaction with the hydrated electron was investigated on two classes of protein: the horse myoglobin and the mussel metallothioneins. We have successively studied the influence of the pH value of metmyoglobin solutions (pH 6, 7 and 8) and the influence of the metals nature (Zn,Cu,Cd) bound to metallothioneins. For both protein, whatever the experimental conditions, the pressure does not influence the value of the reduction rate constant in the investigated range (0.1-100 MPa).