Pulse detection methods

The pump-probe concept can be extended, of course, to other methods for detection. Zewail and co-workers [16,18, 19 and 2Q, 93] have used the probe pulse to drive population from a reactive state to a state that emits fluorescence [94, 95, 96, 97 and 98] or photodissociates, the latter situation allowing the use of mass spectrometry as a sensitive and selective detection method [99, 100]. 

Many experimental methods may be distinguished by whether and how they achieve time resolution—directly or indirectly. Indirect methods avoid the requirement for fast detection methods, either by detemiining relative rates from product yields or by transfonuing from the time axis to another coordinate, for example the distance or flow rate in flow tubes. Direct methods include (laser-) flash photolysis [27], pulse radiolysis [28]... 

In this manuscript we will first describe the characteristics of the temperature jumps and the resulting molecular desorption which can be produced by a laser pulse. We then describe how we have implemented FTMS as a detection method in these experiments and present our results on several adsorbate systems. 

A precursor of the studies on electron transfer reactions between short-lived radicals and colloidal particles was the development of a fast pulse radiolysis method to measure. the polarograms of radicals in the 10 s range . After considerable information had been acquired about the electron transfer reactions of a few dozen radicals at the mercury electrode, this compact electrode was replaced by metal colloids somewhat later, by semiconductor colloids These studies led to the detection of the electron-storing properties of certain colloids and of reactions of the stored electrons. 

Many transition metal complexes have been considered as synzymes for superoxide anion dismutation and activity as SOD mimics. The stability and toxicity of any metal complex intended for pharmaceutical application is of paramount concern, and the complex must also be determined to be truly catalytic for superoxide ion dismutation. Because the catalytic activity of SOD1, for instance, is essentially diffusion-controlled with rates of 2 x 1 () M 1 s 1, fast analytic techniques must be used to directly measure the decay of superoxide anion in testing complexes as SOD mimics. One needs to distinguish between the uncatalyzed stoichiometric decay of the superoxide anion (second-order kinetic behavior) and true catalytic SOD dismutation (first-order behavior with [O ] [synzyme] and many turnovers of SOD mimic catalytic behavior). Indirect detection methods such as those in which a steady-state concentration of superoxide anion is generated from a xanthine/xanthine oxidase system will not measure catalytic synzyme behavior but instead will evaluate the potential SOD mimic as a stoichiometric superoxide scavenger. Two methodologies, stopped-flow kinetic analysis and pulse radiolysis, are fast methods that will measure SOD mimic catalytic behavior. These methods are briefly described in reference 11 and in Section 3.7.2 of Chapter 3. 

Pulse radiolysis, using as time-resolved detection methods optical absorption, luminescence, electrical conductivity or electron spin resonance can be expected to give information on the formation of transient or permanent radiation products and on their movement. 

Suppression of instrumental imperfections and/or selection of particular signal components are both based on the technique of phase cycling which exploits the dependence of NMR signals on the variations of the RF phases of the transmitter pulse(s) S (since phase-cycling is used in every branch of NMR, we assume that the reader is acquainted with the technique) (we will provide more information later, while discussing signal detection methods). At this point we just wish to point out that phase-cycling is extensively used in FFC and has to be supported by the console hardware - a requirement which implies pulser control of RF phases. 

A disadvantage of the LR-CPMG detection method is its total insensitivity to field/frequency offset which must be adjusted before a profile measurement and cannot be corrected by means of a simple procedure during an automatic profile measurement. This requires a higher degree of longterm field stability (including any thermal effects) than the other methods. Despite the insensitivity of the technique, in fact, the field may not be allowed to drift too far from resonance where the RF pulses would lose their efficiency (excursions up to about 5 kHz are, however, quite tolerable). 

Fig. 28. FFC Inversion Recovery sequence. In the upper case the sample is first prepolarized in a filed Bp, then switched to the acquisition field Ba where the first RF pulse of 180° is applied and the sample magnetization is inverted. The field is then switched to B,. and the sample is allowed to relax for the variable time t. Finally, the field is switched again to the acquisition value and the magnetization is sampled by any of the sample-detection methods (here, a simple FID following a 90° RF pulse). Notice that, as shown in the lower diagram, in the special case when Bp = Ba it is possible to neatly avoid the extra switching interval prior to the inversion pulse.

In this chapter, firstly, a very brief survey is given of recent advances in such studies as classified according to the detection technique of transient species in pulse radiolysis. Secondly, examples are chosen from our recent investigations, with special emphasis on the important contributions of pulse radiolysis methods to gas-phase collision dynamics one is electron attachment, the other is Penning ionization and related processes. The detection techniques and corresponding reaction processes, together with major references, are given below ... 

Laser flash photolysis methods have also been applied to the study of nitrenium ion trapping rates and hfetimes. This method relies on short laser pulses to create a high transient concentration of the nitrenium ion, and fast detection technology to characterize its spectrum and lifetime The most frequently used detection method is fast UV-vis spectroscopy. This method has the advantage of high sensitivity, but provides very little specific information about the structure of the species being detected. More recently, time-resolved infrared (TRIR) and Raman spectroscopies have been used in conjunction with flash photolysis methods. These provide very detailed structural information, but suffer from lower detection sensitivity. 

Figure 19.1. Schematic diagram of a general pump-probe-detect laser spectrometer suitable for picosecond electronic absorption, infrared (IR) absorption, Raman, optical calorimetry, and dichroism measurements. For picosecond fluorescence—a pump-detect method, no probe pulse needs to be generated.

Recently, new methods have been developed for very precise quantification of tomatine in tomato plants [13, 48-50]. Thus, Friedman and Levin, used HPLC with a pulse amperometric detection method, for the direct analysis of tomatine in different parts of tomato plants. They found 0.134 % in roots, 0.287 % in stems, 0.567% in calyxes, 0.64% in leaves and 0.745% in flowers [13]. 

Electron spin relaxation in aqueous solutions of Gd3+ chelates is too rapid to be observed at room temperature by the usual pulsed EPR methods, and must be studied by continuous wave (cw) techniques. Two EPR approaches have been used to study relaxation studies of the line shape of the cw EPR resonance of Gd3+ compounds in aqueous solution, and more direct measurement of Tle making use of Longitudinally Detected EPR (LODEPR) [70]. Currently, LODESR is available only at X-band, and the frequency dependence of relaxation is studied by following the frequency dependence of the cw EPR line shape, and especially of the peak-to-peak line width of the first derivative spectrum (ABpp). 

A differential pulse CSV method for the determination of traces of butyltin species in water was compared with two other voltammetric methods, namely differential pulse polarography and ASV (Schwartz et at., 1995). The butyltin species were accumulated on the mercury drop electrode as their tropolone complexes. Detection limits were 5 mg 1 1 for tributyltin (TBT), 0.5 mgl-1 for dibutyltin (DBT) and 0.5 mgl-1 for monobutyltin (MBT). These detection limits were better than the corresponding values obtained in the other analytical methods. 

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