Pulsed flow mechanisms

A discernible trend in modem pump design is towards the use of very small pistons (stroke volume around 100 pi). These tiny pistons have to be operated at very high driving speeds, to provide the flow rates required in analytical HPLC. However, when they are used in combination with electronic feedback pulse control mechanisms, as described above, they can provide extremely stable solvent delivery characteristics. Such is the efficacy of this approach that single piston pumps designed in this way are able to easily out-perform older dual piston pumps, and are consequently beginning to account for a major part of the LC pump market. 

These pumps can be designed with or without a diaphragm. Their operation involves the same mechanism as a cam-drive piston pump, but the movements of the piston are achieved by passing (or not) an electric current through a coiled resistor around the piston [29]. As the solenoid-driven displacement is very abrupt, the pump delivers a pulsed flow [30]. 

In summary, through the use of rapid chemical quench techniques, multiple studies demonstrated the formation of a single tetrahedral intermediate in the reaction pathway of EPSP synthase (Scheme 4, pathway a) which is formed by an attack of the 5-OH group of shikimate-3-phosphate on C-2 of PEP. A complete kinetic and thermodynamic description of this enzyme reaction pathway could be demonstrated, including the isolation and structural elucidation of a tetrahedral enzyme intermediate as originally proposed by Sprinson. This work established the catalytic mechanism and definitively showed that no covalent enzyme—PEP adduct is formed on the reaction pathway. Subsequent work using rapid mixing pulsed-flow ESI—MS studies and solution phase NMR " provides additional support for the catalytic pathway in Scheme 4, pathway a. 

Enzyme reaction intermediates can be characterized, in sub-second timescale, using the so-called pulsed flow method [35]. It employs a direct on-line interface between a rapid-mixing device and a ESI-MS system. It circumvents chemical quenching. By way of this strategy, it was possible to detect the intermediate of a reaction catalyzed by 5-enolpyruvoyl-shikimate-3-phosphate synthase [35]. The time-resolved ESI-MS method was also implemented in measurements of pre-steady-state kinetics of an enzymatic reaction involving Bacillus circulans xylanase [36]. The pre-steady-state kinetic parameters for the formation of the covalent intermediate in the mutant xylanase were determined. The MS results were in agreement with those obtained by stopped-flow ultraviolet-visible spectroscopy. In a later work, hydrolysis of p-nitrophenyl acetate by chymotrypsin was used as a model system [27]. The chymotrypsin-catalyzed hydrolysis follows the mechanism [27] ... 

A new type of hydraulic drive mechanism is used to drive the control rods in HR-200. In the drive system the reactor coolant (water) is the actual medium. The water is pumped into step-cylinders of which the movable parts contain the neutron absorber. A pulsed flow, generated by a controlling magnetic valve in the control unit moves the movable part of the step-cylinder step by step. The drive system is very simple in its stmcture and is designed on the "fail-safe" principle, i.e. all control rods will drop into the reactor core by gravity under loss of electric power, depressurization, postulated breaks in its piping systems and pump shut down events. 

Convection heat transfer is dependent largely on the relative velocity between the warm gas and the drying surface. Interest in pulse combustion heat sources anticipates that high frequency reversals of gas flow direction relative to wet material in dispersed-particle dryers can maintain higher gas velocities around the particles for longer periods than possible ia simple cocurrent dryers. This technique is thus expected to enhance heat- and mass-transfer performance. This is apart from the concept that mechanical stresses iaduced ia material by rapid directional reversals of gas flow promote particle deagglomeration, dispersion, and Hquid stream breakup iato fine droplets. Commercial appHcations are needed to confirm the economic value of pulse combustion for drying. 

Cabelli, D.E. and Bielski, B. (1983). Kinetics and mechanism for the oxidation of ascorbic acid (ascorbate by HO2/O2 radicals. A pulse radiolysis and stopped-flow photolysis study. J. Phys. Chem. 87, 1809. 

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