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Biological Reactions and Kinetics                                                                705


                     H              H                          APPENDIX 22.B: MICHAELIS–MENTEN
                                                               EQUATION
                     j              j
              þ              þ                            þ
               H 3 N---C---R  ! H 3 N---C---CH 2 ---COO  ! NH 4
                                                               As noted, the Monod equation, m ¼ bm[S=(K s þ S)], Equation
                     j              j
                     COO            COO                        22.31, was empirical, based on the observations of bacteria
                  amino acid        glutamate
                                                               cultures. The Monod equation has been referenced in the
                                                      (22:A:1)  literature more frequently than the earlier discovery in 1913
                                                               by Leonor Michaelis and Maud Menten, the latter being given
              Such degradation of amino acids, from protein molecules,  in terms of enzyme kinetics (Stryer, 1981). Its derivation,
            occurs through the treatment process and within the activated-  given in many elementary texts, such as Stryer (1981) and
            sludge reactor with ammonia as an end product. The strategy  Bohinski (1987), is worth reviewing in order to better under-
            of amino acid degradation is to form major metabolic inter-  stand its rationale.
            mediates that can be converted to glucose or be oxidized by
            the Krebs cycle (Stryer, 1981, p. 415).            22.B.1 ENZYME KINETICS

                                                               As with any kinetic formulation, the reaction is the starting
                                                               point. The substrate-to-cell conversion reaction can be
            22.A.2 UREA
                                                               expressed as
            Another source of NH 4 Š, in addition to the breakdown of
                                þ
                           ½
            proteins, depicted in Equation 22.A.1, is urea. Some of the
                                                               substrate þ other reactants þ enzymes $ substrate   enzyme
            NH 4 Š formed in the breakdown of amino acids is used in
                þ
                                                                  ! cells þ end products þ enzymes       (22:B:1)
            ½
            the biosynthesis of nitrogen compounds. In most terrestrial
            vertebrates, the excess NH 4 Š is converted into urea and
                                    þ
                               ½
            then excreted. Humans excrete about 30 g=day of urea, an  where substrate   enzyme is the intermediate substrate–
            amount representing about 80%–90% of the total urine  enzyme complex.
            N (Bohinski, 1987, p. 679). The conversion is by the urea
            cycle, a metabolic pathway through several intermediate
            amino acids, which is also linked to the Krebs cycle.
            The structure of urea is                               BOX 22.B.1   SEARCH FOR A SURROGATE
                                                                              FOR VIABLE CELLS
                                    O                             The total enzyme concentration, E t , represents the total
                                                                  catalytic activity of the system, which is not a measur-
                                    k
                                                                  able quantity. Since viable cells provide the catalytic
                              H 2 N---C---NH 2
                                                                  activity, then a measure of viable cell concentration
            Urea                                                  would work as a good surrogate—or index.
            Bacteria which possess the enzyme urease may convert    In activated-sludge systems, mixed liquor volatile
            urea to ammonia and carbon dioxide as shown by Equation  suspended solids, MLVSS, is an index of catalytic
            22.A.2:                                               activity, easily measurable on a routine basis. The
                                                                  term does not, however, distinguish between viable
                                                                  and nonviable cells. An index more likely to be used
                      O
                                                                  is mixed liquor suspended solids, MLSS. The MLSS is
                      k
                H 2 N---C---NH 2 þ HOH  ! 2NH 3 þ CO 2  (22:A:2)  easier to measure than MLVSS but it includes inert
                                                                  material as well, and so is another step removed from
                                                                  the ideal, a direct measure of catalytic activity. In mak-
            22.A.3 ATP                                            ing the transition from this theoretical ideal to oper-
                                                                  ational kinetics, it is important to bear in mind these
            In driving synthesis, the conversion of ATP to ADP, the
            energy released to drive the biosynthesis is about DG R 8  tacitly assumed proportionalities, i.e., [MLSS]
                                                                  a[MLVSS]; [MLVSS]   a[E t ]. The term X then may
            (ATP ! ADP)   7kJ=mol. The respective structures are
                                                                  represent MLSS or MLVSS—whichever is the desig-
            depicted (Stryer, 1981, p. 240),
                                                                  nation chosen as a system of measurement. The con-
                                                                  stants worked out, however, are associated with one or
                                                                  the other index and cannot be interchanged. The idea of
                        O    O    O               O    O
                                                                  using DNA as a surrogate has also been explored,
                        jj   jj   jj              jj   jj
             Adenosine—O—P—O—P—O—P—O     Adenosine—O—P—O—P—O      starting in the 1960s, but has not supplanted the trad-
                                                                  itional measures. The use of COD was suggested by
                        j    j    j                j   j
                        O    O    O               O    O
               ATP                       ADP                      Orhan and Artan (1994).
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