Experimental Ambiguities

When dealing with pleiotropic respiratory-deficient mutants of yeast, three practical difficulties constantly arise. The major inconvenience is the general genetic instability of the chromosomal pleiotropic respiratory-deficient mutants in S. cerevisiae where an additional p mutation spontaneously arises with very high frequency Since both the nuclear and the mitochondrial mutations are often expressed by deficient cytochromes aas and b, as well as by the loss of oligomycin sensitivity of the ATPase, the biochemical study of these double mutants is very difficult. An easy way out of this difficulty is to use chromosomal respiratory-deficient mutants of a petite-negative yeast species like 5. pombe, where no viable p mutation can be induced. 

Another difficulty is deciding when an enzyme with decreased activity is to be considered deficient. Most of the mitochondrial enzymes activities are decreased to various extents in nonrespiring conditions. As a general rule, we arbitrarily consider an enzyme to be deficient when its activity is lower than 10% of the wild-type under similar physiological conditions. 

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Inspection of the literature shows that branching is clearly indicated for three glucomannans, and a linear backbone for four. It should, however, be noted that the evidence obtained by this method is far more equivocal when no branching is indicated, because part of the volatile glycosides of tetra-O-methyl-D-glucose and -n-mannose is readily lost, whereas their presence in an excess of that required by a linear structure could scarcely be ascribed to any experimental ambiguity. 

The reactivity ratios of a copolymerization system are the fundamental parameters in terms of which the system is described. Since the copolymer composition equation relates the compositions of the product and the feedstock, it is clear that values of r can be evaluated from experimental data in which the corresponding compositions are measured. We shall consider this evaluation procedure in Sec. 7.7, where it will be found that this approach is not as free of ambiguity as might be desired. For now we shall simply assume that we know the desired r values for a system in fact, extensive tabulations of such values exist. An especially convenient source of this information is the Polymer Handbook (Ref. 4). Table 7.1 lists some typical r values at 60°C. 

Figure 5 Schematic representation of a Cartesian dynamics protocol starting from random torsion angles. The weights for non bonded (i.e., van der Waals) interactions, unambiguous distance restraints, and ambiguous distance restraints are varied independently. The covalent interactions are maintained with full weight, co.aie - for the entire protocol. Weights for other experimental terms may be varied in an analogous way. Coupling constant restraints and anisotropy restraints are usually used only in a refinement stage.

In previous studies, the main tool for process improvement was the tubular reactor. This small version of an industrial reactor tube had to be operated at less severe conditions than the industrial-size reactor. Even then, isothermal conditions could never be achieved and kinetic interpretation was ambiguous. Obviously, better tools and techniques were needed for every part of the project. In particular, a better experimental reactor had to be developed that could produce more precise results at well defined conditions. By that time many home-built recycle reactors (RRs), spinning basket reactors and other laboratory continuous stirred tank reactors (CSTRs) were in use and the subject of publications. Most of these served the original author and his reaction well but few could generate the mass velocities used in actual production units. 

A kinetic scheme that is fully consistent with experimental observations may yet be ambiguous in the sense that it may not be unique. An example was discussed earlier (Section 3.1, Consecutive Reactions), when it was shown that ki and 2 in Scheme IX may be interchanged without altering some of the rate equations this is the slow-fast ambiguity. Additional examples of kinetically indistinguishable kinetic schemes have been discussed.The following subsection treats one aspect of this problem. 

The accurate composition of the gas hydrates for a long time remained a controversial subject, since direct analysis leads to ambiguous results owing to decomposition of the hydrate and/or inclusion of mother liquor in the crystals. Thus it was firmly believed that the nonstoichiometric compositions of gas hydrates found experimentally were all due to errors in the analysis. But more recent determinations of the composition by the indirect... 

None of the procedures outlined can claim any strict justification. Indeed, the deviations of experimental curves from the calculated ones based on simple assumptions can be due in general to a number of causes, some of which were dealt with in Section II.A. A principal ambiguity lies in the choice of whether to treat such departures in terms of either variable Ed or kd, and in the former case often whether the changes in Ed are to be attributed to nonequivalence of adsorption sites, or to lateral interactions between the adsorbed particles, or to yet some other factor (98). 

Triad information is more powerful, but typically is subject to more experimental error and signal assignments are often ambiguous (Section 7.3.3.12). Triad data for the MMA-S system are consistent with the terminal model and support the view that any penultimate unit effects on specificity are small.Mv lS... 

Activation energy values for the recombination of the products of carbonate decompositions are generally low and so it is expected that values of E will be close to the dissociation enthalpy. Such correlations are not always readily discerned, however, since there is ambiguity in what is to be regarded as a mole of activated complex . If the reaction is shown experimentally to be readily reversible, the assumption may be made that Et = ntAH and the value of nt may be an indication of the number of reactant molecules participating in activated complex formation. Kinetic parameters for dissociation reactions of a number of carbonates have been shown to be consistent with the predictions of the Polanyi—Wigner equation [eqn. (19)]. 

Conversion of Earno into an absolute (UHV) scale rests on the values of ff-0 and for Hg used as areference surface. While the accuracy of is indisputable, the experimental value of contact potential difference between Hg and H20, are a subject of continued dispute. Efforts have been made in this chapter to try to highlight the elements of the problem. However, a specialized experimental approach to the measurement of 0 (and A0 upon water adsorption) of Hg would definitely remove any further ambiguity as well as any reasons not to accept certain conclusions. 

The crucial test of all of the theories based on solvation would be the absence of the isokinetic relationship in the gas phase, but the experimental evidence is ambiguous. Rudakov found no relationship for atomization of simple molecules (6), whereas Riietschi claimed it for thermal decomposition of alky] chlorides (96) and Denisov for several radical reactions (107) however, the first series may be too inhomogeneous and the latter ones should be tested with use of better statistics. A comparison of the same reaction series in the gas phase on the one hand and in solution on the other hand would be most desirable, but such data seem not to be available. 

Qualitative relaxation-studies have also been reported for an extensive series of derivatives of inositols, pentopyranoses, l,6-anhydro-/3-D-hexopyranoses, furanoses, and septanoses. In all instances, the experimentally determined Ri(ns) values reflect the anticipated geometry. For the furanose derivatives especially, they provide a better means for distinguishing between epimeric pairs than the relatively ambiguous interpretation of coupling-constant data. 

Haim S has commented on the ambiguities inherent in the interpretation of rate laws, using the V(IIl)-l-Cr(II) reaction as an example. The experimental rate law found by Espenson ... 

A certain ambiguity arises in the proper choice of the thermodynamic parameter p, since entropy changes due to solvent orientation are neglected. The available experimental data (cf. Sect. 4) indicate, however, that the free energy of reaction for systems showing a spin change is close to zero. The numerical analysis has been therefore performed for the specific case p = 0, for which value the rate constant in Fig. 15 has been computed as a function of S and h lkgT. 

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