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quickly becomes so large that the molecules do not have enough energy to move any closer together The steric interaction (repulsion) keeps them apart This illustrates the general principle that attractions occur where the potential energy is minimal or decreasing, and repulsions occur when the potential energy increases This is an important concept to remember The potential energy function depicted in Fig 6-13 is called the Lennard-Jones potential, named for John Lennard-Jones who first proposed it in 1924 as a mathematical model to describe two neutral atoms approaching each other
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The highly polar character of water makes for interesting interactions between water and nonpolar substances The statement oil and water don t mix comes to mind The interaction between water and a nonpolar substance like oil is called the hydrophobic effect or hydrophobic interaction The interaction does not involve a single, physical force Nonetheless hydrophobic interactions are sometimes also called hydrophobic forces, because the hydrophobic effect forces molecules to arrange themselves in a way that minimizes the contact between water and the nonpolar substance Thus, water and oil separate, forming two separate phases; this minimizes the amount of contact between oil molecules and water molecules The driving force behind hydrophobic interactions is the fact that water likes to form hydrogen bonds Hydrogen bonding between water and itself or between water and other polar molecules lowers the potential energy It is thus energetically favorable When a nonpolar or hydrophobic molecule is placed into water, it takes up space between the water molecules restricting their ability to hydrogen bond with each other There is a price to pay for this in terms of free energy First, there is the enthalpy needed to break some of the hydrogen bonds between the water molecules Second, although hydrogen bonding in water represents a highly ordered, low-entropy state for the molecules (since they must line up with particular orientations to bond with each other), the presence of a nonpolar (hydrophobic) molecule actually decreases the entropy of the water Remember order in this context is inversely related to the number of ways of doing something More order means fewer ways of doing something (less entropy) Less order means more ways of doing the same thing (more entropy) Water molecules by themselves are free to rotate and form hydrogen bonds in many orientations But, at the surface of a nonpolar or hydrophobic molecule, where the water comes in contact with the hydrophobic molecule, steric interactions restrict the water from rotating freely
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chapter 6 F o r c e s A F F e c t i n g c o n F o r m At i o n i n B i o L o g i c A L m o L e c U L e s
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FIguRE 6-14 Water molecules at the surface of a hydrophobic molecule have their movement limited by steric interactions; this in turn limits the possibilities for hydrogen bonding with other water molecules
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Figure 6-14 illustrates water molecules at the surface of a hydrophobic molecule The water molecules orient themselves with the hydrogen atoms toward the hydrophobic surface This orientation allows the water to come as close as possible to the hydrophobic molecule, while at the same time exposing only the most neutral side of the water molecule toward the hydrophobic surface In this orientation, the surface water is restricted from rotating freely due to steric interactions This restricted rotation then limits the possible angles for hydrogen bonds to form between the surface water molecules and other water molecules in solution, thus decreasing the entropy of water that is closest to the surface water This close-to-the-surface water, however, is free to rotate and will do so if it can favorably break the hydrogen bonds with the surface water and make them with other water molecules in solution (As a side note, we can explain why this is the most neutral side of the water molecule First, the partially positive charge on this side of the molecule is split between the two hydrogen atoms, and separated by the large angle between them This makes the charge effectively weaker in this orientation Second, the large angle between the hydrogen atoms exposes some of the electronegative oxygen on that side of the molecule as well This further neutralizes the amount of charge that is exposed on that side of the water molecule) Recall Eq (4-13), shown here as Eq (6-14) DG = DH T DS (6-14)
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