Paired-Fraction Electrochemical Programming of Aqueous Peptide-Chain Assembly

Peptide-chain assembly in water is constrained by the competition between productive aminolysis or ligation and hydrolysis, enzyme deactivation, substrate precipitation, and time-dependent product cleavage. This paper formulates a target-independent version of paired-fraction electrochemical programming (PFEP) in which anodic and cathodic liquids are generated outside the reaction vessel, analytically released, and metered into an electrode-free ligation reactor. PFEP is not proposed to condense unactivated amino acids. Its proposed function is to impose a measured trajectory of acid-base capacity, ionic composition, and, where chemically justified, redox capacity around an established activated-donor or enzyme-catalysed bond-forming reaction. A kinetic model links pH-dependent aminolysis and hydrolysis to cumulative qualified fraction dose. Synthetic demonstration data predict an assay-corrected product yield of 74.8% for a programmed trajectory versus 62.1% for an optimized static comparator at equal substrate loading. These values are not measurements. A causal experiment, chemical-reconstruction control, power calculation, mass-balance requirement, and falsification rules are specified. Article type: Original theoretical research with synthetic model data and a prospective validation protocol. All numerical results labelled synthetic or modelled are hypothesis-illustration and planning outputs, not experimental measurements. No validated process, clinical benefit, or shelf life is claimed.