Both the oxidized and reduced forms of Hipip (high-potential iron--sulphur protein) are reduced (approx. 30% yields) by eaq.- in a single-stage process, rate constants 1.7 x 10(10) and 1.8 x 10(10) M-1 . s-1 respectively, at 25 degrees C, pH 7.0 (5 mM-phosphate). Super-reduced Hipip, which is formed in the latter case, has a spectrum which closely resembles that of reduced ferredoxin, i.e. Fe4S...

Pulse radiolysis was applied to study the reactivity of *OH radicals with procarbazine (PC), a cytostatic agent widely used in radiation- and chemotherapy. An overall rate constant of k(*OH+PC) = 3.7 x 10(9) l.mol(-1).s(-1) was determined. The thereby formed transients had a strong absorption at 350 nm, epsilon350 = 4.46 x 10(3) l.mol(-1).cm(-1), and a weak absorption band around 530 nm. Comput...

The pulse radiolysis method has been used to generate and study a series of fivecarbocations, consisting of phenylcarbenium ions and cyclopropylphenylcarbenium ions, in chlorocarbon solvents. Rate constants for the reactions of these substituted carbenium ions with various nucleophiles such as halide ions, alkyl amines, amonia and water, have been determined. The observed reactivity trends (or,...

The pulse radiolysis of N(2)O saturated aqueous solutions of KSCN was studied under neutral pH conditions. The observed optical absorption spectrum of the SCN(*) radical in solution is more complex than previously reported, but it is in good agreement with that measured in the gas phase. Kinetic traces at 330 and 472 nm corresponding to SCN(*) and (SCN)(2)(*-), respectively, were fit using a Mo...

At the Argonne Chemistry Division efforts are underway to develop a sub-picosecond electron beam pulse radiolysis facility for chemical studies. The target output of the accelerator is to generate electron pulses that can be adjusted from 3nC in .6ps to 100nC in 45ps. In conjunction with development of the accelerator a stateof-the-art ultrafast laser system is under construction that will driv...

Numerous additives are used in the electrolytes of lithium-ion batteries, especially for formation an efficient solid electrolyte interphase at surface electrodes. Understanding degradation processes these compounds is thus important; they can be seen through radiolysis. In case fluoroethylene carbonate (FEC), picosecond pulse radiolysis experiments evidenced FEC.- . This radical stabilized nea...

Using a pulse radiolysis approach to generate and observe superoxide anions (O2-.) in the absence and presence of calcium, we have attempted to verify the recent hypothesis of Babizhayev (Arch. Biochem. Biophys. 266, 446-451, 1988) of a Ca2(+)-O2-. interaction during lipid peroxidation. We could not observe rapid scavenging of O2-. or complex formation with Ca2+ to account for an inhibitory eff...