Intrinsic contrast parameters

A magnetization filter consists of modulated rf excitation, for example, from a sequence of nonselective rf pulses with given flip angles and given pulse separations. These parameters of the pulse sequence are adjustable, and they determine the characteristics of the filter, that is, they can be used to tune the filter transfer function. Therefore, they are referred to as extrinsic contrast parameters. They must be discriminated from the intrinsic contrast parameters, which are the NMR parameters specific of the sample under investigation and are related to the material properties [Manl]. Therefore, the parameter vectorp in the weight factor of eqn (7.1.2) is separated into two parts, a vector Pe of extrinsic parameters and a vectorPj(r) of intrinsic parameters. 

The contrast parameters relevant to material characterization through NMR imaging are the intrinsic NMR parameters of the sample. They are referred to as the contrast parameters per se. They can be divided into chemical and physical parameters, and into molecular, mesoscopic, microscopic, and macroscopic parameters. A list of NMR parameters for contrast in NMR imaging is compiled in Table 7.1.1. 

Contrast in NMRI depends on both material-specific and operator-selected parameters. The material-specific parameters include the spin density and the relaxation times Tj and T2. The operator-selected parameters include the pulse sequence (inversion recovery, spin-echo, etc.) and the pulse delay and repetition times (timing parameters). For a given imaging system and pulse sequence, it is the delay and repetition times in conjunction with the intrinsic material parameters which dictate the appearance of the final image. If the correct pulse sequence is employed and the relaxation times of the two materials are known, it is possible to calculate the delay and/or repetition times that will produce the maximum diflerence in signal intensity between those materials. 

However, in many practical situations the problem exists that effective rate constants and activation energies have been derived on the basis of laboratory experiments. The question arises then as to whether or not these parameters arc influenced by transport effects. With the relations given so far, this question cannot be answered yet, since according to its definition by cq 27 the Thiele modulus is based on the intrinsic rate constant k. This problem can be solved by introducing a new modulus, which in contrast to only contains observable (effective) quantities, and thus can... 

The measurement of ket for single electron-transfer reactions is of particular fundamental interest since it provides direct information on the energetics of the elementary electron-transfer step (Sect. 3.1). As for solution reactants, standard rate constants, k t, can be defined as those measured at the standard potential, E, for the adsorbed redox couple. The free energy of activation, AG, at E°a is equal to the intrinsic barrier, AG t, since no correction for work terms is required [contrast eqn. (7) for solution reactants] [3]. Similarly, activation parameters for surface-attached reactants are related directly to the enthalpic and entropic barriers for the elementary electron-transfer step [3],... 

The relative stabilities of substituted benzyl cations [21C ] are correlated by equation (27) with a high resonance demand parameter Tq = 1.29 (Mishima et al., 1987, 1995). The linear correlation for the whole range of substituents down to the 3,5-(Cp3)2 group (Fig. 27), contrasts with the concave Y-T plot (Fig. 7) of the solvolytic reactivities of [21]. Note that the Tq value for the gas-phase stabilities of [21C ] is identical with the r value assigned for the SnI solvolysis of [21] tosylates hence, the r value of 1.29 must be an intrinsic index inherent in [21C ], rather than a correlational artifact of a non-linear relationship for the complex solvolysis mechanism. 

We have seen that the local constraint on the surface curvatures, set by the surfactant parameter, can be treated within the context of differential geometry, which deals with the intrinsic geometry of the surface. In contrast, the global constraint, set by the composition of the mixture, is dependent upon the extrinsic properties of the surface, which need not be related to its intrinsic characteristics. (For example, the surface to volume ratio of a set of parallel planes can assume any value by suitably tuning the spacing bebveen the planes. Similarly, the ratio of surface area to external volume i.e. the volume of space outside each sphere closer to that sphere than any other) of a lattice of spheres depends upon the separation between the spheres.)... 

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