Silane-based pretreatment coatings exemplify boundary connectivity in corrosion protection. Bis-sulfur silanes (BTSE) form dense Si-O-Me networks on metals while exposing hydrophobic organic chains, creating dual interfacial barriers. Electrochemical tests show these coupling agents reduce corrosion current density by 3-4 orders of magnitude compared to untreated substrates. Novel zwitterionic silanes now enable pH-responsive self-healing coatings that reconnect boundary interfaces through dynamic bond reconfiguration under environmental stress.