Abstract. Mass action systems capture chemical reaction networks in homogeneous and dilute solutions. We suggest a notion of generalized mass action systems that admits arbitrary power-law rate functions and serves as a more realistic model for reaction networks in intracellular environments. In addition to the complexes of a network and the related stoichiometric subspace, we introduce corresponding kinetic complexes, which represent the exponents in the rate functions and determine the kinetic-order subspace. We show that several results of Chemical Reaction Network Theory carry over to the case of generalized mass action kinetics. Our main result essentially states that, if the sign vectors of the stoichiometric and kinetic-order subspace coincide, there exists a unique complex balancing equilibrium in every stoichiometric compatibility class. However, in contrast to classical mass action systems, multiple complex balancing equilibria in one stoichiometric compatibility class are possible in general.
We give necessary and sufficient conditions in terms of sign vectors for the injectivity of families of polynomial maps with arbitrary real exponents defined on the positive orthant. Our work relates and extends existing injectivity conditions expressed in terms of Jacobian matrices and determinants. In the context of chemical reaction networks with power-law kinetics, our results can be used to preclude as well as to guarantee multiple positive steady states. In the context of real algebraic geometry, our work recognizes a prior result of Craciun, Garcia-Puente, and Sottile, together with work of two of the authors, as the first partial multivariate generalization of the classical Descartes' rule, which bounds the number of positive real roots of a univariate real polynomial in terms of the number of sign variations of its coefficients.
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