Rate-determined sensors

Radical ions, 33, 44 Raman spectroelectrochemistry, 45 Randles-Sevcik equation, 31 Rate constant, 12, 18 Rate determining step, 4, 14 Reaction mechanism, 33, 36, 113 Reaction pathway, 4, 33 Reaction rate, 12 Receptor-based sensors, 186 Redox recycling, 135... 

Moos, R., Reetmeyer, B., HiirJand, A. and Plog, C. (2006) Sensor for directly determining the exhaust gas recirculation rate — EGR sensor. Sens. Actuators B,... 

The active site of organophosphorus hydrolase (OPH) contains two metal atoms (zinc in the wild-type enzyme) and catalyzes hydrolysis of numerous organophos-phate compounds including pesticides as well as chemical warfare agents such as sarin and soman. Rates of OPH catalyzed hydrolysis of organophosphates exceed those of chemical hydrolysis by NaOH at 4°C by factors of 40 to 2450 [41-43]. The enzyme has been described for use in sensor systems with exceptional detection limits reported for response times on the order of 10 seconds [44-48]. However, the presence of OP/CWA is detected by the inhibition of enzymatic rate determined by comparing rate measnrements in the presence and absence of the analyte. 

Recent experiments on Sn02 [437] show that the picture is more compUcated For small particles, the portion of the interfacial reaction succeeding the sensor action is rate determining, and not the diffusion step. (Then the statement V/ie- 0 may be violated.)... 

The concentration of the indicated material (substrate or product) at the indicator electrode surface under steady state conditions depends on the Michaelis constants, the activity of the biologically active compound in the membrane, the thickness of this membrane, and the diffusion coefficients of the substrate and product. It can be shown that for any given system, the response time of the enzyme electrode is given by the ratio d lD (d = layer thickness D = effective diffusion coefficient), except if the rate-determining step is the diffusion of a gas through a gas-permeable membrane, as in the case of the membrane-covered gas sensors. In practice layer thickness as low as 30 jit can be used. Depending on the substrate concentration, response times between 10 seconds and 15 minutes can be achieved. 

The special design of the Latham bowl allows for a specific blood cell separation known as SURGE. This technique makes use of the principle of critical velocity. The Latham bowl is filled until the huffy coat, ie, layer of platelets and white cells, moves in front of the bowl optics. At this point the machine starts to recirculate plasma through the bowl at increasing rates. The smallest particles, ie, platelets, ate the first to leave the bowl. Their high number causes the effluent line to turn foggy. The optical density of the fluid in the effluent line is monitored by the line sensor. A special algorithm then determines when to open and close the appropriate valves, as well as the optimum recirculation rate. 

Enzyme Immunosensors. Enzyme immunosensors are enzyme immunoassays coupled with electrochemical sensors. These sensors (qv) require multiple steps for analyte determination, and either sandwich assays or competitive binding assays maybe used. Both of these assays use antibodies for the analyte of interest attached to a membrane on the surface of an electrochemical sensor. In the sandwich assay type, the membrane-bound antibody binds the sample antigen, which in turn binds another antibody that is enzyme-labeled. This immunosensor is then placed in a solution containing the substrate for the labeling enzyme and the rate of product formation is measured electrochemically. The rate of the reaction is proportional to the amount of bound enzyme and thus to the amount of the analyte antigen. The sandwich assay can be used only with antigens capable of binding two different antibodies simultaneously (53). 

The sensor is the element of an instrument directly influenced by the measured quantity. In temperature measurement the thermal mass (capacity) of the sensor usually determines the meter s dynamics. The same applies to thermal anemometers. In IR analyzers used for concentration measurement, the volume of the flow cell and the sample flow rate are the critical factors. Some instruments, like sound-level meters, respond very fast, and follow the pressure changes up to several kHz. 

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