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formed in thea,b-elimination reaction can react with indole to give tryptophan, or pyruvate and ammonia (one off-aromacompound in broccoli and cauliflower). If serine is replaced with cystine the products are H2S, NH3, pyruvate and thiolcysteine.H2S and NH3 are the two major off-aroma compounds of broccoli.Alliinase is the key enzyme in aroma and flavor development in onions and garlic when they are cut or mashed. Alliinase is aPALP-requiring enzyme. The substratesS-1-propenyl-L- cysteine sulfoxide andS-allyl-L-cysteine sulfoxide undergoa,beliminationby alliinase to produce 1-propenylsulfenic acid (a lachrymator) or allysulfenic acid which then nonenzymatically formsthearoma and flavor components of onions and garlic, respectively [113].7.6.4 Inorganic lonsBoth cations and anions can serve as cofactors. The cations include Ca2+, Mg2+, Zn2+, Fe2+, Cu2+, Co, andothers. The anions include Cl-, Br-, F-, and I, among others.The cations may be involved directly in catalysis, as shown earlier for yeast alcohol dehydrogenase (Fig. 26), in binding of-substrate to the active site, in maintaining the conformation and stability of the substrate, such as Ca2+2+ ina-amylase, or as part ofthe substrate, such as MgATP as required by kinases.Zn2+2- inEscherichia coli milk alkaline phosphatase (APase) will be used as an example because Zn is a major essential cationin enzyme systems. Alkaline phosphatase requires four Zn2+
+
, Ni
ions per molecule of enzyme (80,000 MW). Two of the Zn
serve
a structural function, helping to hold the two subunits of the enzyme together (maintaining quaternary structure). The other two
Zn
2+
are located in the two active sites of the enzyme, where the role of the Zn
is as a “super acid” group to activate the SerOH
group involved in the hydrolysis of the
p
-nitrophenylphosphate
substrate:
2+
2+
, Na
+
, K
+
2+
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