3 × 1015 1.3 × 1015 – Step 2 in two-step functionalization Carbodiimide coupling of dye 2.0 × 1015 1.07 × 1015 0.93 × 1015 One-step functionalization Electrochemical grafting of dye by amine oxidation for 8 min 0.9 × 1015 – 0.9 × 1015 Conclusions DWCNT membranes were successfully functionalized with dye for ionic rectification by electrooxidation of amine in a single step. Non-faradic (EIS) spectra indicated that the functionalized gatekeeper by one-step modification can be actuated to mimic the

protein channel under bias. This functional chemistry was proven to be highly effective on the enhancement of ion rectification, wherein the highest experimental rectification factor of ferricyanide was up to 14.4. The control experiments supported that the observed rectification was a result click here of transmembrane ionic current instead of electrochemical reaction of ferricyanide. With the decreasing size of ion, we have observed smaller rectification due to partially blocked ion channels. The rectification was decreased with the higher ionic concentration. It suggested that the rectification is attributed to both charge and steric effects at low concentration, while the steric effect PRN1371 supplier is dominant at high concentration. After removing the dye, the DWCNT-dye membrane

exhibited no enhancement of rectification. This control experiment supported that the rectification was induced by functionalized dye molecules. The saturated functionalized dye density by a single step was quantified at 2.25 × 1014 molecules/cm2 on glassy carbon by dye assay, the same as that of two-step functionalization. However, no apparent change of rectification learn more was observed for two-step functionalization. The dye molecules on the membrane by single-step functionalization are more responsive to the applied bias due to direct grafting on the conductive surface instead of the grafted organic layer. Another possible reason is that the actual yield

of the second step of the two-step modification on CNT membranes may be much less than the calculated 18% yield on glassy carbon. One-step functionalization by electrooxidation of amine provides a simple and promising functionalization chemistry for the application of CNT membranes. Acknowledgments This work was supported by NIDA, #5R01DA018822-05, DOE EPSCoR, DE-FG02-07ER46375, and DARPA, W911NF-09-1-0267. Critical infrastructure provided by the University of KY Center for Nanoscale Science and Engineering. Electronic supplementary material Additional file 1: Figure S1: Schematic rectification setup. Working electrode (W.E) is DWCNT membrane coated with 30-nm-thick Pd/Au film; reference/counter electrode (R.E/C.E) is Ag/AgCl electrode.