Selected reaction monitoring purpose

To ensure that appropriate resolution and lack of interference is obtained during method development, it is highly recommended actively monitoring PLs and aware of the retention/elution times and intensity of the PLs relative to the retention/elu-tion times for the analytes of the interest. Table 2 summarizes several representative Selective Reaction Monitoring (SRM) transitions for PLs monitoring purpose during method development. 

For purposes of quantitative analysis, selected ion monitoring (SIM) and selected reaction monitoring (SRM) are two commonly utilized approaches. The latter is also referred to as multiple reaction monitoring (MRM). In both modes, considerable structural information is lost nonetheless, these techniques are extremely powerful for target compound quantihcation in biological matrices, if the compound of interest is known. 

For the detection, a tandem mass spectrometer Quattro Micro API ESCI (Waters Corp., Milford, MA) with a triple quadrupole was employed. The instrument was operated in electrospray in the positive ionization mode (ESI+) with the following optimized parameters capillary voltage, 0.5 kV source block temperature, 130 °C nebulization and desolvation gas (nitrogen) heated at 400 °C and delivered at 800 L/h, and as cone gas at 50 L/h collision cell pressure, 3 x 1(F6 bar (argon). Data was recorded in the multiple reaction monitoring (MRM) mode by selection of the two most intense precursor-to-product ion transitions for each analyte, except for the ISs, for which only one transition was monitored. The most intense transition for each analyte was used for quantitative purposes. Table 2 shows MRM transitions, cone voltages and collision energies used for the analysis of the antidepressants included in the LC-MS/MS method. 

Production of the API begins with the selection of a synthetic route, as determined in the development program. Raw materials are added into a reaction vessel. These raw materials as reactants are heated or cooled in the reaction vessel (normal range is from -15 to 140 °C purpose-built vessels are needed for extreme reactions that require lower or higher temperature controls or pressurization of reaction processes). The chemical synthesis reactions are monitored and controlled via sensor probes (pH, temperature, and pressure) with in-process feedback controls for adjustments and alarms when necessary. Samples are withdrawn at dehned intervals for analysis to determine the reaction progress. Catalysts, including enzymes, may be added to speed up and direct the reaction along a certain pathway. 

The purpose of this section is to demonstrate the reaction rate constant and selectivity of a bimolecular reaction may be influenced by solute-solute clustering as the pressure is lowered towards the critical point. The solvent sensitive photodimerization of 2-cyclohexen-l-one is an ideal candidate as both the rate of dimerization and the product selectivity may be monitored. 

The active site responsible for the aerobic oxidation of alcohols over Pd/AljO, catalysts has long been debated [96-lOOj. Many reports claim that the active site for this catalyst material is the metallic palladium based on electrochemical studies of these catalysts [100, 101]. On the contrary, there are reports that claim that palladium oxide is the active site for the oxidation reaction and the metalhc palladium has a lesser catalytic activity [96,97). In this section, we present examples on how in situ XAS combined with other analytical techniques such as ATR-IR, DRIFTS, and mass spectroscopic methods have been used to study the nature of the actual active site for the supported palladium catalysts for the selective aerobic oxidation of benzylic alcohols. Initially, we present examples that claim that palladium in its metallic state is the active site for this selective aerobic oxidation, followed by some recent examples where researchers have reported that ojddic palladium is the active site for this reaction. Examples where in situ spectroscopic methods have been utilized to arrive at the conclusion are presented here. For this purpose, a spectroscopic reaction cell, acting as a continuous flow reactor, has been equipped with X-ray transparent windows and then charged with the catalyst material. A liquid pump is used to feed the reactants and solvent mixture into the reaction cell, which can be heated by an oven. The reaction was monitored by a transmission flow-through IR cell. A detailed description of the experimental setup and procedure can be found elsewhere [100]. Figure 12.10 shows the obtained XAS results as well as the online product analysis by FTIR for a Pd/AljOj catalyst during the aerobic oxidation of benzyl alcohol. 

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