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321 mediated electron transfer to a solution species has to be considered. A practically important situation occurs when the mediated electron transfer is faster than the charge transfer reaction of the same solution species on a bare electrode. If the charge transfer reaction at the electrode surface (which regenerates the original form of the mediator) is also faster, we speak about an electron-transfer-mediated electrocatalysis. Since 1975, hundreds of papers dealing with chemically modified electrodes have appeared in the literature. The initial effort in this topic was reviewed by Murray in 1984. In subsequent years, the interest in surface modification gradually decreased. The reason might be that the rather demanding preparative techniques of chemical modification result, naturally, in a product possessing all the disadvantages of a two-dimensional (monolayer) system. The number of the redox-mediator turnovers, needed for sufficiently high electrode currents, is, therefore, relatively very large. For instance, the mediated current of 1 A/cm 2 would require (for a typical mediator coverage F = 10~10mol/cm2), the turnover rate nt: n^j/FT^lO's-1 (5.5.35)

REFindNoCase()

If returnSubexpressions is TRUE, returns a structure containing two arrays named len and pos that contain the lengths and positions of each case-insensitive match. If returnSubexpressions is FALSE, returns an integer containing the position of the case-insensitive match, or zero if no match.

REFindNoCase( regularExpression, string, start, returnSubexpressions)

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which is beyond the practically available values. The surface modified electrodes may also be rapidly deactivated by the mediator desorption or decomposition as well as by adsorption of impurities from the electrolyte. Therefore, recent interest has been focused prevailingly on electrodes modified by a multilayer coverage, which can easily be achieved by using polymer films on electrodes. In this case, the mediated electron transfer to solution species can proceed inside the whole film (which actually behaves as a system with a homogeneous catalyst), and the necessary turnover rate is relatively lower than in a monolayer. A discussion of the charge transfer reaction on the polymer-modified electrode should consider not only the interaction of the mediator with the electrode and a solution species (as with chemically modified electrodes), but also the transport processes across the film. Let us assume that a solution species S reacts with the mediator Red/Ox couple as depicted in Fig. 5.32. Besides the simple charge transfer reaction with the mediator at the interface film/solution, we have also to include diffusion of species S in the polymer film (the diffusion coefficient D Sp , which is usually much lower than in solution), and also charge propagation via immobilized redox centres in the film. This can formally be described by a diffusion coefficient Dp which is dependent on the concentration of the redox sites and their mutual distance (cf. Eq. (2.6.33). The charge propagates in the film by electron hopping between the polymer Red/Ox couples. This is controlled by the electrode potential only in a close proximity of the electrode; in more distant sites, the charge transport is driven by a concentration gradient of reduced or oxidized mediators. The observed faradaic current density, j F , is a superposition of

CREATE TRIGGER tU_OrderItem ON OrderItem AFTER Update AS BEGIN /* Declare variables for use by the trigger */ DECLARE @iOldQuantity INTEGER, @iNewQuantity INTEGER, @sOldItemNumber VARCHAR(15),

Listing 11-6 (continued)

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Fig. 5.32 Scheme of the reduction of a solution species Sox within the polymer film. Electron transfer is mediated by the immobilized redox active sites Red/Ox

@sNewItemNumber VARCHAR(15) /* Get the old ordered quantity and item number */ SELECT @iOldQuantity = Quantity, @sOldItemNumber = ItemNumber FROM Deleted /* Get the new ordered quantity and item number */ SELECT @iNewQuantity = Quantity, @sNewItemNumber = ItemNumber FROM Inserted /* Update the old item number to put the former ordered quantity back into inventory */ UPDATE InventoryItem SET AvailableToSell = AvailableToSell + @iOldQuantity WHERE ItemNumber = @sOldItemNumber /* Update the new item number (it might have changed) to remove the new ordered quantity from inventory */ UPDATE InventoryItem SET AvailableToSell = AvailableToSell - @iOldQuantity WHERE ItemNumber = @sNewItemNumber END

This trigger code executes only once and uses only the values from the first row in the Deleted pseudotable, in turn causing only one row in the InventoryItem table to be updated. Consider, however, the trigger code in Listing 11-7.

these two contributions: diffusion of S and electron hopping in the film:

AFTER Update AS BEGIN /* Put the old ordered quantity back into inventory */ UPDATE InventoryItem SET AvailableToSell = AvailableToSell + d.Quantity FROM Deleted d INNER JOIN InventoryItem ii ON d.ItemNumber = ii.ItemNumber /* Remove the new ordered quantity from inventory Remember: the item number may have changed! */ UPDATE InventoryItem SET AvailableToSell = AvailableToSell - i.Quantity FROM Inserted i INNER JOIN InventoryItem ii ON i.ItemNumber = ii.ItemNumber END

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