Straightforward functionalization of breath figures: simultaneous orthogonal host-guest and pH-responsive interfaces
Alberto Sanz de León,1 Alexandra Muñoz-Bonilla,2* Alberto Gallardo,1Alfonso Fernandez-Mayoralas,3 Julien Bernard,4 Juan Rodríguez-Hernández1*
Instituto de Ciencia y Tecnología de Polímeros (ICTP), Consejo Superior de Investigaciones Científicas (CSIC), C/Juan de la Cierva 3, 28006 Madrid, Spain. Email: email@example.com
Departamento de Química Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid, C/Francisco Tomás y Valiente 7, Cantoblanco, 28049 Madrid, Spain. Email: firstname.lastname@example.org
Instituto de Química Orgánica General, CSIC, Juan de la Cierva 3, 28006, Madrid, Spain.
Université de Lyon, Lyon, F-69003, France ; INSA-Lyon, IMP, Villeurbanne, F-69621, France; CNRS, UMR 5223, Ingénierie des Matériaux Polymères, Villeurbanne, F-69621, France.
Displacement of the Ada groups using a guest molecule with higher affinity: NSS
We studied the possibility of displacing the Ada-PAA85 molecules inside the CD of the pores. We used two different approaches. One, a done with Ada-FAm (depicted in the manuscript) a displacement with a solution containing 1.0 mg/mL of free CD was employed. In a parallel series of experiments, a solution containing 1.0 mg/mL of sodium 2-naphthalene sulfonate (NSS) was used. Naphtalenes are aromatic molecules which, in average, present higher affinity by the CD than adamantanes . As a consequence, NSS would go inside the cavities of the CD of the PS-CD inside the pores, releasing the Ada- PAA85 towards the solution thus increasing the hydrophobicity of the surface of the surface (Figure S1b).
Figure S1. a) Scheme of the displacement of Ada-PAA85 by NSS moieties: (i) unmodified surface, (ii) surface modified with a solution of 1.0 mg/mL of Ada-PAA85 for 24 h, (iii) surface after substitution of previously immobilized Ada-PAA85 with a solution of 1.0 mg/mL of NSS for 24h; b) CA values of the three steps ((i), (ii), (iii)) depicted above.
Desorption of the Ada-PAA85/PLL-FITC complex
Experiments to undo the host-guest interaction between the CD immobilized in surface and the Ada of the Ada-PAA85, without breaking the electrostatic interaction between the PAA and PLL-FITC was done. The same solution containing 1.0 mg/mL CD as before was incubated for 24 h to release the complex Ada-PAA85//PLL-FITC. In this case, the decrease in fluorescence intensity values show only partial desorption from the surface. This detachment is not as high as in the case of the liberation of Ada-FAm or the variation of pH to protonate the PAA chains and liberate the PLL-FITC. However, in this case the system is much more complex, as the CD has to pass first through an electrostatic bilayer of PAA-PLL before reaching to the Ada linked to the surface.
Figure S2. Fluorescence micrograph of Surface S2 a) after subsequent immobilization of Ada-PAA85 and PLL-FITC and b) after desorption of Ada-PAA85//PLL-FITC by adding a solution containing 1 mg/mL CD for 24 h; c) Fluorescence intensity of the micrographs.