Probing the influence of X-rays on aqueous copper solutions using time-resolved in situ combined video/X-ray absorption near-edge/ultraviolet-visible spectroscopy

Time-resolved in situ video monitoring and ultraviolet-visible spectroscopy in combination with X-ray absorption near-edge spectroscopy (XANES) have been used for the first time in a combined manner to study the effect of synchrotron radiation on a series of homogeneous aqueous copper solutions in a microreactor. This series included both non biologically relevant ( pyridine, bipyridine, neocuproine, terpyridine, dimethylpyridine, ammonia, ethylenediamine, and 1,10-phenanthroline) and biologically relevant ( histidine, glycine, and imidazole) ligands. It was found that when water is present as solvent, gas bubbles are formed under the influence of the X-ray beam. At the liquid-gas interface of these bubbles, in particular cases colloidal copper nanoparticles are formed. This reduction process was found to be influenced by the type of copper precursor salt (SO42-, NO3-, and Cl-), the ligands surrounding the copper cation, and the redox potential of the copper complexes ( ranging between +594 and -360 mV). In other words, in some cases, no reduction was encountered (e.g., ammonia in the presence of SO42- and NO3-), whereas in other cases reduction to either Cu+ (neocuproine with SO42-) or CuO (e.g., histidine and imidazole both with SO42-, NO3-, and Cl-) was observed. These results illustrate the added value of video spectroscopy for the interpretation of in situ XANES studies. Not only do the results give an illustration of the parameters that are important in the redox processes that occur in biological systems, they also show the potential problems associated with studying catalytic processes in aqueous solutions by XANES spectroscopy

Observing the influence of X-rays on aqueous copper solutions by in situ combined video/XAFS/UV-Vis spectroscopy

In situ video monitoring and UV-Vis spectroscopy have been used in combination with XAFS spectroscopy to study the effect of synchrotron radiation on a series of copper solutions in a micro-reactor. The samples that were investigated contained initially a mixture of Cu2+ ions and both biologically and non-biologically relevant amine ligands. It was observed that when water was used as the solvent, gas bubbles are formed under the influence of the X-ray beam. At the resultant liquid-gas interface and under certain conditions, colloidal copper nanoparticles were observed to form. This reduction process was influenced primarily by the type of the copper precursor salt (SO42-, NO3- and Cl-), although the ligands surrounding the copper cation and the redox potential of the copper complexes (ranging between +594 and 360 mV) were also observed to have some effect. Critically we show how these results illustrate the benefits of combining methods (and in particular the use of video imaging) to monitor chemical processes and for observing the influence of one technique on the measurement process. Furthermore the results give some insight into the parameters that are important in the redox-processes that occur in biological systems