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88        Metabolism



             Enzymes: basics
                                                              C. Enzyme classes
             Enzymes are biological catalysts—i. e., sub-     More than 2000 different enzymes are cur-
             stances of biological origin that accelerate     rently known. A system of classification has
             chemical reactions (see p. 24). The orderly      been developed that takes into account both
             course of metabolic processes is only possible   their reaction specificity and their substrate
             because each cell is equipped with its own       specificity. Each enzyme is entered in the En-
             genetically determined set of enzymes. It is     zyme Catalogue with a four-digit Enzyme
             only this that allows coordinated sequences      Commission number (EC number). The first
             of reactions (metabolic pathways;see p.112).     digit indicates membership of one of the six
             Enzymes are also involved in many regulatory     major classes. The next two indicate sub-
             mechanisms that allow the metabolism to          classes and subsubclasses. The last digit indi-
             adapt to changing conditions (see p.114). Al-    cates where theenzymebelongs in thesub-
             most all enzymes are proteins.However,           subclass. For example, lactate dehydrogenase
             there are also catalytically active ribonucleic  (see pp. 98–101) has the EC number 1.1.1.27
             acids, the “ribozymes” (see pp. 246, 252).       (class 1, oxidoreductases; subclass 1.1, CH–OH
                                                              group as electron donor; sub-subclass 1.1.1,
                                                                     +
                                                              NAD(P) as electron acceptor).
             A. Enzymatic activity
                                                                 Enzymes with similar reaction specificities
             The catalytic action of an enzyme, its activity,  are grouped into each of the six major classes:
             is measured by determining the increase in          The oxidoreductases (class 1) catalyze the
             the reaction rate under precisely defined con-   transfer of reducing equivalents from one re-
             ditions—i. e., the difference between the turn-  dox system to another.
             over (violet) of the catalyzed reaction (or-        The transferases (class 2) catalyze the
             ange) and uncatalyzed reaction (yellow) in a     transfer of other groups from one molecule
             specific time interval. Normally, reaction rates  to another. Oxidoreductases and transferases
             are expressed as the change in concentration     generally require coenzymes (see pp.104ff.).
                                            –1
             per unit of time (mol  1  –1   s ;see p. 22).       The hydrolases (class 3) are also involved in
             Since the catalytic activity of an enzyme is     group transfer, but the acceptor is always a
             independent of the volume, the unit used         water molecule.
             for enzymes is usually turnover per unit time,      Lyases (class 4, often also referred to as
                                             –1
             expressed in katal (kat, mol  s ). However,      “synthases”) catalyze reactions involving ei-
             the international unit U is still more com-      ther the cleavage or formation of chemical
                                                 –1
             monly used (µmol turnover  min ;1 U =            bonds, with double bonds either arising or
             16.7 nkat).                                      disappearing.
                                                                 The isomerases (class 5)movegroups
                                                              within a molecule, without changing the
             B. Reaction and substrate specificity
                                                              gross composition of the substrate.
             The action of enzymes is usually very specific.     The ligation reactions catalyzed by ligases
             This applies not only to the type of reaction    (“synthetases,” class 6) are energy-dependent
             being catalyzed (reaction specificity), but also  and are therefore always coupled to the hy-
             to the nature of the reactants (“substrates”)    drolysis of nucleoside triphosphates.
             that are involved (substrate specificity;see
             p. 94). In Fig. B, this is illustrated schemati-    In addition to the enzyme name, we also
             cally using a bond-breaking enzyme as an         usually give its EC number. The annotated
             example. Highly specific enzymes (type A,        enzyme list (pp. 420ff.) includes all of the en-
             top) catalyze the cleavage of only one type      zymes mentioned in this book, classified ac-
             of bond, and only when the structure of the      cording to the Enzyme Catalog system.
             substrate is the correct one. Other enzymes
             (type B, middle) have narrow reaction specif-
             icity, but broad substrate specificity. Type C
             enzymes (with low reaction specificity and
             low substrate specificity, bottom) are very
             rare.


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