Abstract: Provided herein are methods of increasing the enzymatic rate of hydrolysis of starch substrates. In certain embodiments the method comprises contacting a starch substrate with one or more amylase family enzymes in the presence of greater than 0.001 mM manganese ions. In certain embodiments, the method comprises contacting a starch substrate with one or more glucoamylase and/or ?-amylase enzymes in the presence of greater than 0.001 mM calcium ions (Ca++). In certain embodiments, the method comprises contacting the starch substrate with a ?-amylase in the presence of greater than 0.001 mM manganese ion, calcium ion, magnesium ion (Mg++), strontium ion (Sr++), barium ion (Ba++) or any combination of said metal ions. In certain embodiments the method comprises contacting the starch substrate with a glucoamylase in the presence of greater than 0.001 mM manganese ion, calcium ion, lithium ion (Li+), potassium ion (K+), or any combination of said metal ions.