Particular aspects of the present invention provide compositions and methods for modulating intracellular signal transduction, including modulation of at least one of membrane structure, membrane potential or membrane conductivity, membrane proteins or receptors, ion channels, and calcium dependant cellular messaging systems, comprising use of the inventive electrokinetically generated solutions to impart electrochemical and/or conformational changes in membranous structures (e.g., membrane and/or membrane proteins, receptors or other components) including but not limited to G-protein coupled receptors (GPCRs) and/or G-proteins, and intracellular junctions. In particular embodiments, the electrokinetically generated solutions or compositions are gas-enriched and/or comprise other therapeutic agents. Other embodiments include particular therapeutic methods comprising administration or formulations of the therapeutic compositions, and in various combination treatments.