| Summary: | Constructing molecular assembly between a soluble cyclodextrin polymer (SCDP) and an anticorrosive component is conducive to increasing the availability of a corrosion inhibitor with low molecular polarity in aqueous solution. The SCDP was prepared via the weak crosslinking effect of glutaraldehyde using β-cyclodextrin as the subunit, whose structure was confirmed by proton nuclear magnetic resonance spectra (<sup>1</sup>H NMR), X-ray diffraction and morphology. An assembly between SCDP (host) and <i>trans</i>-cinnamaldehyde (guest, CA) was constructed, and the intermolecular interactions were disclosed by Fourier transform infrared spectra (FTIR). The corrosion inhibition of SCDP/CA assembly for mild steel in 3.5% NaCl solution was assessed through electrochemical and surface analyses. <sup>1</sup>H NMR results showed that exterior hydroxyls of β-cyclodextrin were the active sites for crosslinking. Hydrogen bonds might be the binding force between SCDP and CA according to FTIR analyses. Electrochemical measurements revealed that SCDP/CA assembly could suppress both cathodic and anodic reactions and enhance the polarization impedance for mild steel in the corrosive medium with a maximum efficiency of 92.2% at 30 °C. Surface analyses showed that CA molecules could be released from the assembly followed by the energy competition mechanism, and solely adsorb on the steel surface in parallel form, which was further evidenced by theoretical modeling.
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