Chemical marker definition

An important goal of studies with intermediate- and short-term biomarkers is validation of the markers by demonstrating their correlation with definitive endpoints. It is reasonable to expect that these biomarkers will enable differences in human susceptibilities to exogenous chemicals to be detected, or suspected, at an early stage of exposure, and the liability of susceptible persons to be predicted long before the definitive endpoint is reached. It follows that studies using such biomarkers could be accomplished in a much shorter time and at a much lower cost than those aimed at determining definitive end-points. 

NIR analysts often use a statistical methodology called chemometrics to calibrate an NIR analysis. Chemometrics is a specialized branch of mathematical analysis that uses statistical algorithms to predict the identity and concentration of materials. Chemometrics is heavily used in NIR spectral analysis to provide quantitative and qualitative information about a variety of pure substances and mixtures. NIR spectra are often the result of complex, convoluted, and even unknown interactions of the different molecules and their environment. As a result, it is difficult to pick out a spectral peak or set of peaks that behave linearly with concentration or are definitive identifiable markers of particular chemical structures. Chemometrics uses statistical algorithms to pick out complex relationships between a set of spectra and the material s composition and then uses the relationship to predict the composition of new materials. Essentially, the NIR system, computer, and associated software are trained to relate spectral variation to identity and then apply that training to new examples of the material. 

The Kirkendall effect is a well-known phenomenon resulting from the difference in intrinsic diffusivities of chemical constituents of substitution solid solutions (non-reciprocal diffusion). Many textbooks provide a detailed and quantitative treatment of this important phenomenon (Philibert, 1991) schematized in Fig. 2.2 for a homogeneous diffusion couple of constituents A and B forming a continuous substitutional solid solution. In Fig. 2.2a, the initial position of the contact surface is marked by fixed inert markers that define the origin, also named the Matano plane (M), of the reference frame centred on the mass or the number of moles this reference frame is conunonly used to define interdiffusion processes and the unique interdiffusion coefficient that permits the characterization of the transport of A and B. Moving inert markers determine the actual position of the initial contact surface (Fig. 2.2b) and therefore visualize the drift of lattice planes within the diffusion zone. They mark the origin, also named the Kirkendall plane, of the lattice-fixed frame of reference that permits the definition of the different intrinsic diffusion coefficients of the A and B constituents. Relative to the Matano plane, this drift of lattice planes is equivalent to a translation of the diffusion couple without apparent deformation and without the action of any externally applied stress or, in other words, to a rigid body translation of the phase lattice. 

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