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28        Basics



             Hydrophobic interactions                         is therefore positive (the disorder in the water
                                                              increases), and the negative term –T   ∆S
             Water is an excellent solvent for ions and for   makes the separation process exergonic
             substances that contain polarized bonds (see     (∆G < 0),so thatitproceeds spontaneously.
             p. 20). Substances of this type are referred to
             as polar or hydrophilic (“water-loving”). In     C. Arrangements of amphipathic substances
             contrast, substances that consist mainly of
                                                              in water
             hydrocarbon structures dissolve only poorly
             in water. Such substances are said to be apolar  Molecules that contain both polar and apolar
             or hydrophobic.                                  groups are called amphipathic or amphiphilic.
                                                              This group includes soaps (see p. 48), phos-
                                                              pholipids (see p. 50), and bile acids (see p. 56).
             A. Solubility of methane
                                                                 As a result of the “oil drop effect” amphi-
             To understand the reasons for the poor water     pathic substances in water tend to arrange
             solubility of hydrocarbons, it is useful first to  themselves in such a way as to minimize the
             examine the energetics (see p.16) of the pro-    area of surface contact between the apolar
             cesses involved. In (1), the individual terms of  regions of the molecule and water. On water
             the Gibbs–Helmholtz equation (see p. 20) for     surfaces, they usually form single-layer films
             the simplest compound of this type, methane,     (top) in which the polar “head groups” face
             are shown (see p. 4). As can be seen, the tran-  toward the water. Soap bubbles (right) consist
             sition from gaseous methane to water is ac-      of double films, with a thin layer of water
                                   0
             tually exothermic (∆H < 0). Nevertheless, the    enclosed between them. In water, depending
                                              0
             change in thefreeenthalpy ∆G is positive         on their concentration, amphipathic com-
             (the process is endergonic), because the en-     pounds form micelles—i. e., spherical aggre-
             tropy term T   ∆S  0  has a strongly positive    gates with their head groups facing toward
             value. The entropy change in the process         the outside, or extended bilayered double
                0
             (∆S ) is evidently negative—i. e., a solution of  membranes. Most biological membranes are
             methane in water has a higher degree of order    assembled according to this principle (see
             than either water or gaseous methane. One        p. 214). Closed hollow membrane sacs are
             reason for this is that the methane molecules    known as vesicles. This type of structure
             areless mobilewhen surroundedbywater.            serves to transport substances within cells
             More importantly, however, the water around      and in the blood (see p. 278).
             the apolar molecules forms cage-like “clath-        The separation of oil and water (B)can be
             rate” structures, which—as in ice—are stabi-     prevented by adding a strongly amphipathic
             lized by H bonds. This strongly increases the    substance.Duringshaking,a more or less
             degreeoforder in the water—and themoreso         stable emulsion then forms, in which the sur-
             the larger the area of surface contact between   face of the oil drops is occupied by amphi-
             the water and the apolar phase.                  pathic molecules that provide it with polar
                                                              properties externally. The emulsification of
                                                              fats in food by bile acids and phospholipids
             B. The “oil drop effect”
                                                              is a vital precondition for the digestion of fats
             The spontaneous separation of oil and water,     (see p. 314).
             a familiar observation in everyday life, is due
             to the energetically unfavorable formation of
             clathrate structures. When a mixture of water
             and oil is firmly shaken, lots of tiny oil drops
             form to begin with, but these quickly coalesce
             spontaneously to form larger drops—the two
             phases separate. A larger drop has a smaller
             surface area than several small drops with the
             same volume. Separation therefore reduces
             the area of surface contact between the water
             and the oil, and consequently also the extent
             of clathrate formation. The ∆S for this process


           Koolman, Color Atlas of Biochemistry, 2nd edition © 2005 Thieme
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