Human Metabolism. Keith N. Frayn

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Название Human Metabolism
Автор произведения Keith N. Frayn
Жанр Медицина
Серия
Издательство Медицина
Год выпуска 0
isbn 9781119331469



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of methane has the three-dimensional structure shown in Figure 1.3a. The outer electron ‘cloud’ has a very even distribution over the four hydrogen atoms, all of which have an equal tendency to pull electrons their way. The molecule has no distinct electrical poles – it is non-polar. Because of this very even distribution of electrons, molecules near each other have little tendency to interact. In contrast, in the water molecule (Figure 1.3b) the oxygen atom has a distinct tendency to pull electrons its way, shifting the distribution of the outer electron cloud so that it is more dense over the oxygen atom, and correspondingly less dense elsewhere. Therefore, the molecule has a rather negatively charged region around the central oxygen atom, and correspondingly positively charged regions around the hydrogen atoms. Thus, it has distinct electrical poles – it is a relatively polar molecule. It is easy to imagine that water molecules near to each other will interact. Like electrical charges repel each other, unlike charges attract. This gives water molecules a tendency to line up so that the positive regions of one attract the negative region of an adjacent molecule (Figure 1.3b). So, water molecules, unlike those of methane, tend to ‘stick together’: the energy needed to break them apart and form a gas is much greater than for methane, and hence water is a liquid while methane is a gas. The latent heat of evaporation of water is 2.5 kJ g−1, whereas that of methane is 0.6 kJ g−1. Note that the polarity of the water molecule is not as extreme as that of an ion – it is merely a rather uneven distribution of electrons, but enough to affect its properties considerably.

      The contrast between water and methane may be extended to larger molecules. Organic compounds composed solely of carbon and hydrogen – for instance, the alkanes or ‘paraffins’ – all have the property of extreme non-polarity: the chemical (covalent) bond between carbon and hydrogen atoms leads to a very even distribution of electrons, and the molecules have little interaction with each other. A result is that polar molecules, such as those of water, and non-polar molecules, such as those of alkanes, do not mix well: the water molecules tend to bond to each other and to exclude the non-polar molecules, which can themselves pack together very closely because of the lack of interaction between them. In fact, there is an additional form of direct attraction between non-polar molecules, the van der Waals forces. Random fluctuations in the density of the electron cloud surrounding a molecule lead to minor, transient degrees of polarity; these induce an opposite change in a neighbouring molecule, with the result that there is a transient attraction between them. These are very weak attractions, however, and the effect of the exclusion by water is considerably stronger. The non-polar molecules are said to be hydrophobic (water fearing or water hating).

      Ionic compounds, the extreme examples of polarity, are not confined to inorganic chemistry. Organic molecules may include ionised groups. These may be almost entirely ionised under normal conditions – for instance, the esters of orthophosphoric acid (‘phosphate groups’), as in the compounds AMP, ADP, and ATP, in metabolites such as glucose 6-phosphate, and in phospholipids. Most of the organic acids involved in intermediary metabolism, such as lactic acid, pyruvic acid, and the long-chain carboxylic acids (fatty acids), are also largely ionised at physiological hydrogen ion concentrations (Box 1.1). Thus, generation of lactic acid during exercise raises the hydrogen ion concentration (the acidity) both within the cells where it is produced, and generally within the body, since it is released into the bloodstream.

      The normal pH in blood plasma is around 7.4. (It may be somewhat lower within cells, down to about 6.8.) This corresponds to a hydrogen ion concentration of 3.98 × 10−8 mol l−1 (since – log10 of 3.98 × 10−8 is 7.4).

      The equation for ionisation of an acid HA is:

      this equilibrium is described by the equation:

      where Ki is the dissociation or ionisation constant and is a measure of the strength of the acid: the higher the value of Ki the stronger (i.e. the more dissociated) the acid.

      Ki in the equation above relates the concentrations expressed in molar terms (e.g. mol/l). (Strictly, it is not the concentrations but the ‘effective ion concentrations’ or ion activities which are related; these are not quite the same as concentrations because of inter-ion attractions. In most biological systems, however, in which the concentrations are relatively low, it is a close approximation to use concentrations. If activities are used, then the symbol Ka is used for the dissociation constant of an acid.)

      The calculation is done as follows (using acetic acid as an example):