Metal rapid time-response

Despite the considerable amount of information that has been garnered from more traditional methods of study it is clearly desirable to be able to generate, spectroscopically characterize and follow the reaction kinetics of coordinatively unsaturated species in real time. Since desired timescales for reaction will typically be in the microsecond to sub-microsecond range, a system with a rapid time response will be required. Transient absorption systems employing a visible or UV probe which meet this criterion have been developed and have provided valuable information for metal carbonyl systems [14,15,27]. However, since metal carbonyls are extremely photolabile and their UV-visible absorption spectra are not very structure sensitive, the preferred choice for a spectroscopic probe is time resolved infrared spectroscopy. Unfortunately, infrared detectors are enormously less sensitive and significantly slower... 

Rapid Time-Response of Metal ion-Sensing Systems... 

The deactivation of bifunctional reforming catalysts is mainly due to the deposition of coke on the metal and the acid sites. Coking on the metallic function is responsible for the rapid initial deactivation which is also accompanied by changes in the selectivity of products formed on its surface. The acidic function deactivates more gradually with time as a result of the add site fouling by coke coverage. 

Figure 37.4 Replicate Pseudo-nitzschia multiseries cultures were grown under 24 h light (100 tmol photons s ) at 15 °C for 4 days as an auxostat (chemostat with growth limited by pump rate) with Si-limited f/2 media. On day -4, the pumps were turned off, forcing the cultures into Si-limitation. On days 0, 4 Si-spikes (10 pM) were added. On day 5, trace-metals (f/2 stock) was added, with no apparent response. Optical density (cell abundance) and variable fluorescence were determined from a PAM fluorometer and are plotted versus time (dashed vertical lines indicate additions of unenriched seawater dashed horizontal line indicates maximal Fv/Fm values in healthy cells). A rapid decline and recovery of variable fluorescence indicates impaired photosynthetic performance, and functionally mimics the response of Fe-limitation, with recovery times dependent on the length of time spent in Si-deprived conditions.

Lastly, electron transfer in D—[H]—A assemblies is not a perquisite of the excited states of metal complexes. Organic ensembles 38 and 39 (R = SiMe2 Bu), containing a dimethylaniline-anthracene redox pair, have been synthesized recently [124]. Preliminary time-resolved and steady-state fluorescence experiments indicate the occurrence of photoinduced electron transfer. In work related to Watson Crick base-paired systems, the excited state of the fluorescent pyrene derivative 40 is efficiently quenched (94-99 %) by 2 -deoxyguanosine (dG), 2 -deoxycytidine (dC), or 2 -deoxythymidine (dT) in aqueous solution [125]. A PCET mechanism is thought to be responsible for this process, as the thermodynamics of electron transfer are unfavorable unless coupled to a rapid proton-transfer step. The quenched lifetime of 40 in the presence of dC and dT in H2O is significantly extended by a factor of 1.5-2.0 in D2O this isotope effect is similar to that observed in the kinetics studies of 1 [70]. The invoked PCET reaction mechanism also accounts for the inability of dC and dT to quench the fluorescence of 40 in the aprotic organic solvent DMSO. 

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