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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

image of the porous lms obtained from the in situ structure inversion is shown in Fig 523 The inset in the same gure shows the SEM image of the sphere arrays before the solvent treatment After the solvent treatment, the sphere array directly transforms to the porous lm, which also exhibits the characteristic pattern of the hexagonal close-packed array The average pore diameter (150724 nm), which is estimated from 540 randomly selected pores in SEM images, is obviously smaller than the average sphere size The distance between the pore centers is 250720 nm The AFM image of the porous lms is shown in Fig 524, which further con rms the morphology observed by SEM The pore sizes and the distance between the pore centers are consistent with those observed by SEM.

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

The spectroscopic methods show that the porous structures and the colloidal arrays are composed of the same polymer (Li et al, 2006c) As discussed in Section 54, the colloidal spheres can be stretched to form nonspherical colloids such as ellipsoidal colloids by Ar+ laser irradiation The array of the ellipsoidal colloids is obtained by exposing the colloidal sphere array to a polarized Ar+ laser beam for 10 min The lms with elliptical pores can be obtained from the array of the ellipsoidal colloids after the same annealing treatment Figure 525 shows the SEM images of the array of the ellipsoidal colloids and the corresponding porous lm formed from the structure inversion The average axial ratio of the colloids and pores are 146 and 125 The smaller axial ratio for the pores could be attributed to the stress relaxation occurring in the structure inversion process.

TCMP Tightly coupled multiprocessing describes a mainframe multiprocessing complex in which processors share real memory and virtual storage disk, and utilize high-speed inter-processor communications TCO Total cost of ownership is a financial measurement which includes hard and soft costs over a period of time (typically three years).

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

As discussed earlier, the porous structures and the colloidal arrays are composed of the same polymer indicated by spectroscopic analysis This con rms that the porous lms are formed through a solvent-induced in situ structure.

jF/nF = DSp(ds/dx)0 - Dp(dr/djc)0

and is used to evaluate purchase decisions, including not only purchase costs (CapEx) but also ongoing costs (OpEx) TCP Transmission Control Protocol is the session layer (layer 4) of the Internet protocol (IP) suite It guarantees reliable, in-order delivery of data from sender to receiver It is more commonly referred to as TCP/IP TOE TCP Offload Engine is a hardware implementation of the TCP/IP stack placed on a network interface card (NIC) to offload the TCP/IP processing from the central CPU to the NIC This is done to increase both TCP/IP performance and CPU cycles available for business applications token ring LAN technology that was developed by IBM in the early 1980s It was standardized by the IEEE (8025) but lost most of the market to Ethernet in the early 1990s topologies Network topologies are configurations of components on a network.

Figure 5.24. Typical AFM image and fast Fourier transform (FFT) plot of the mesoporous lms formed by the in situ sphere pore inversion. Source: From Li et al., 2006c.

(5.5.36)

transceiver A device with both a transmitter (outgoing) and receiver (incoming) in one TTY Teletype was originally a physical typewriter with a communications channel that was used as an early output device for messaging systems such as Western Union It was subsequently used as an input/output device for early mainframes, and then as a mainframe device-type specification for line-by-line terminals two-way Two processors on a blade: a main processor and a coprocessor Typically, one processor is used for computing and one is used for I/O USB Universal Serial Bus is a standard serial bus used to communicate between computers and other devices V2P Virtual-to-physical is the migration of an entire operating environment from a virtual environment to a physical computer V2V Virtual-to-virtual is the migration of an entire operating environment (OS, applications, and data) from one virtual system to another virtual system.

(s and r are the concentrations of species S and Red/Ox sites, respectively). The solution of Eq. (5.5.36) may differ for various particular situations and boundary conditions, but we can phenomenologically describe the mediated charge transfer process in the polymer film by an effective heterogeneous rate constant kp and the concentration of S in solution, cs: