Sensitivity relationships

This means, in practice, that when employing a polar solvent with n-heptane (or any other paraffin for that matter) to reduce the retention, there will be a dramatic reduction in retention over the concentration range of about 0-2%w/v. However, subsequent changes in solute retention with polar solvent concentration will be relatively small. This will be true for any polar solute and was experimentally verified by Scott and Kucera for solutions of ethyl acetate, tetrahydrofuran and n-propanol in n-heptane. The very sensitive relationship between solvent concentration and retention at very low concentrations makes the phase system very difficult to make reproducible. This problem is one of the factors that deter analysts from using silica gel as a stationary phase for the separation of polar solutes. It is very satisfactory, however, for the separation of polarizable and weakly polar substances that can be eluted by paraffin/methylene dichloride or similar types of solvent mixtures. 

In the case of a linear response without offset, the previous sensitivity relationships simplify to ... 

In these three cases, we have kept the structure of the acid component constant and varied the alcohol part with surprising results. This is another example of the sensitive relationship between chemical structure and biological properties. The relationship between structure and aroma can be understood pretty well at the molecular level. We return to this issue in chapter 25. 

The chemistry behind the detonation of organic compounds is exceedingly complex and poorly understood, because it involves a variety of intermolecular reactions different from those observed during thermolysis in solution or in the gas phase [92-94], The conditions required to induce detonation of organic explosives vary widely and no clear-cut structure-sensitivity relationship exists. Nevertheless, most known explosives contain characteristic functional groups, and small molecules containing several of these should be handled with great care. 

P. Politzer, J.S. Murray, P. Lane, P. Sjoberg, H.G. Adolph, Shock-sensitivity Relationships for Nitramines and Nitroaliphatics, Chem. Phys. 

The various structure-sensitivity relationships mentioned above typically treat different classes of compounds separately. Nitramines, for example, are not expected to fit on the same correlations as nitroaromatics or nitroheterocycles. Even within a given class, however, a variety of decomposition mechanisms may be operative. Indeed, Kamlet and Adolph found it necessary to establish two oxidant balance correlations for nitroaromatics [16], one being only for molecules having a CH—containing substituent alpha to a nitro group, 3 ... 

Sensitivity Relationship between the sensor s output and input, so that changes in output correspond to changes in input, often generating a constant. 

Law, K. Y, Tarnawsky, J. I. W. and Popovic, Z. D. (1994). Azo pigments and their intermediates—a study of the structure-sensitivity relationship of photogenerating bisazo pigments in bilayer xerographic devices. J. Imag. Sci. Technol, 38, 118-24. [204]... 

Franot, C., Roberts, D.W., Basketter, D.A., Benezra, C. and Lepoittevin, J.-P. (1994) Structure-activity relationships for contact allergenic potential of Y,Y-dimethyl-Y-butyrolactone derivatives. 2. Quantitative structure-skin sensitization relationships for cxrSubstituted-a-methyl-Y,Y-dimethyl-y-butyrolactones. Chem. Res. Toxicol.,... 

Yoshimoto A, Tobe H, Johdo O, Ishikura T, Takeuchi T. Structure sensitivity relationship of anthiacycline antibiotics to C7-reduction by redox enzymes, J Antibiot 1991 44 287—295. 

No simple correlation has been found in the structure-cross-sensitivity relationships, and hymenin (89) shows no cross sensitivity with the diastereomer parthenin. 

In this chapter we will briefly survey some of the most commonly used measures of sensitivity, as well as some earlier correlations between sensitivity and molecular properties. This will provide a basis for further discussion of factors affecting sensitivities and the subsequent presentation of correlations developed in our laboratory. It is often the exceptions to structure-sensitivity relationships that offer the greatest promise in broadening our understanding of the reactivities of energetic compounds. Studies of several exceptional systems will be presented and discussed in the light of unique structural or reactive features which can account for their observed behavior. 

ITie success of this nitramine shock sensitivity relationship [Table 2 and eq. (4)] prompted us to investigate whether eq. (4) would serve also for nitro phatics. Table 3 lists shock sensitivities and some structural parameters for five nitroaliphatics. Again, no correlation was found to exist between shock sensitivity and either Ri or Rave, where Ri and Rave are, respectively, the longest C-NO2 distance and the average of all C-NO2 (and N-NO2) bond lengths in the molecule. However, an excellent correlation between shock sensitivity and the quantity (n/M)Rave was found, with a linear correlation coefficient of 0.98 [36]. 

Kamlet, M.J. (1960) "Sensitivity Relationships , Third Symposium (International) on Detonation, Office of Naval Research, Washington, DC, pp. 13-34. 

Acosta, R., Granados, J., Mourelle, M., Perez-Alvarez, V. and Quezada, E., 1989. Sulfite sensitivity relationship beteween sulfite plasma levels and bronchospasm case report. Ann Allergy 107, 263-267. 

Stumm, C., J.M.H. Hermans, E.J. Middlebeek, A.F. Croes G.J.M. De Vries. 1977. Killer sensitive relationships in yeasts from natural habitats. Antonie van Leeuwenhoek 43 125-128. 

Quantity-quality characteristics. The numbers in Table 2 are somewhat biased by the different conversion rates. As stated above, the percentages refer to the number of structures converted by the individual programs and not to the total number of 639 X-ray structures in the study. Thus, there is a sensitive relationship between conversion rate and quality. 

It is clear from these discussions that the development of detailed models of biochemical processes and the investigation of their sensitivity relationships may have important applications in improving our understanding of disease and in developing treatments. Not surprisingly, therefore, a great detail of effort is being... 

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