Hydrogen-bonded multilayers of micelles of a dually responsive dicationic block copolymer

Erel Göktepe, İrem
Tuncer, Cansel
Butun, Vural
Demirel, A. Levent
We report the fabrication of hydrogen-bonded multilayers of micelles of a dually responsive, dicationic block copolymer, poly[2-(N-morpholino)ethyl methacrylate-block-2-(diisopropylamino)ethyl methacrylate] (PMEMA-b-PDPA). By taking advantage of the difference in the hydrophilicity of PMEMA and PDPA blocks, micelles with a PMEMA-corona and a PDPA-core were obtained above pH 6.5 and were assembled layer-by-layer at the surface with tannic acid (TA) at pH 7.4 through hydrogen bonding interactions between morpholino units of PMEMA and hydroxyl groups of TA. Destruction of PMEMA-b-PDPA micelles/TA films could be controlled at both acidic and basic conditions. At basic pH (pH = 8.75), multilayers disintegrated due to ionization of TA and disruption of hydrogen bonding interactions between layers of micelles and TA. At moderately acidic pH values, partially dissolved PMEMA-b-PDPA micelles and monomers underwent a restructuring with TA molecules and remained adsorbed at the surface. Complete dissolution of the multilayers occurred at around pH 3.6 due to further protonation of the tertiary amino groups on both blocks of PMEMA-b-PDPA, resulting in a charge imbalance between PMEMA-b-PDPA and TA layers followed by disintegration of the films. We have also encapsulated pyrene in the micellar cores and found that pyrene released from PMEMA-b-PDPA micelles/TA films increased 1.5- and 2.5-fold when the pH was decreased from 7.5 to 6 and 5, respectively. Such an increase in the amount of pyrene released was due to pH-controlled dissolution of the micellar cores. We have also found that at pH 7.5, increasing the temperature to 40 degrees C enhanced the release of pyrene by approximately 2-fold. Such an increase is due to lower critical solution temperature (LCST) behaviour of coronal PMEMA chains leading to temperature-induced conformational changes on the coronal chains, facilitating the release of pyrene through the coronal chains into the solution. Hydrogen bonded multilayers of micelles of a dicationic block copolymer are interesting due to the response of both multilayers and micellar cores at different pH paving the way for multiple pH-controlled delivery of functional molecules from surfaces.


Hydrogen-bonded layer-by-layer films of block copolymer micelles with pH-responsive cores
Erel Göktepe, İrem; Zhuk, Aliaksandr; Sukhishvili, Svetlana A. (Elsevier BV, 2011-03-01)
We report on construction of hydrogen-bonded monolayers and multilayers of micelles of the poly(2-(diethylamino)ethyl methacrylate)-block-poly(N-isopropyl acrylamide) (PDEA-b-PNIPAM) with PNIPAM-corona and polybasic PDEA cores. Films were constructed at pH 7.5 and 25 degrees C to assure the deposition of PDEA-b-PNIPAM in the micellar form. When monolayers of block copolymer micelles (BCMs) were exposed to moderately acidic pH values, micellar cores dissolved, while PDEA-b-PNIPAM remained adsorbed at the sur...
pH-responsive layer-by-layer films of zwitterionic block copolymer micelles
Yusan, Pelin; Tuncel, Irem; Butun, Vural; Demirel, A. Levent; Erel Göktepe, İrem (2014-01-01)
We report a strategy to incorporate micelles of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]-block-poly[2-(diisopropylamino) ethyl methacrylate] (beta PDMA-b-PDPA) into electrostatic layer-by-layer (LbL) films. We obtained micelles with pH-responsive PDPA-cores and zwitterionic bPDMA-coronae at pH 8.5 through pH-induced self-assembly of bPDMA-b-PDPA in aqueous solution. To incorporate bPDMA-b-PDPA micelles into LbL films, we first obtained a net electrical charge on bPDMA-coronae. Nega...
Hydrogen-Bonded Multilayers With Controllable pH-Induced Disintegration Kinetics for Controlled Release Applications From Surfaces
Bağ, Esra; Begik, Oguzhan; Yusan, Pelin; Erel Göktepe, İrem (2015-04-03)
We report on incorporation of coordination complexes into hydrogen-bonded multilayers which was found to be an effective method to control pH-induced disintegration kinetics of hydrogen-bonded multilayers. By taking advantage of the strong metal chelating and hydrogen donating properties of Tannic Acid (TA), coordination complexes of Zr4+ and TA (Zr(IV)-TA complexes) were prepared and then self-assembled at the surface using hydrogen accepting polymers such as poly (N-vinyl caprolactam) (PVCL) or poly(N-iso...
Skin-like self-assembled monolayers on InAs/GaSb superlattice photodetectors
Salihoglu, Omer; Muti, Abdullah; Kutluer, Kutlu; Tansel, Tunay; Turan, Raşit; AYDINLI, ATİLLA (2012-09-12)
We report on the effects of monolayer (ML) thick skin-like octadecanethiol (ODT, CH3[CH2](17)SH) on type-II InAs/GaSb MWIR photodetectors. Circumventing the ageing effects of conventional sulfur compounds, we use ODT, a self-assembling, long molecular chain headed with a sulfur atom. Photodiodes coated with and without the self-assembled monolayer (SAM) ODT were compared for their electrical and optical performances. For ODT-coated diodes, the dark current density was improved by two orders of magnitude at ...
Mixed carboranethiol self-assembled monolayers on gold surfaces
Sohrabnia, Nima; Danışman, Mehmet Fatih; Yılmaz, Ayşen; Department of Chemistry (2017)
Thiolated derivatives of dicarba-closo-dodecaborane, HS-C2B10H11 (carboranethiols, CTs), with icosahedral molecular structure are one of the promising candidates for self-assembled monolayer (SAM) applications. CT SAMs possess various advantages relative to organic counterparts, such as high stability towards chemical, oxidative and thermal degradations as well as having fewer defects. In this study, pure and mixed SAMs of three different positional isomers of carboranethiols (namely M1, O1 and M9) on templ...
Citation Formats
İ. Erel Göktepe, C. Tuncer, V. Butun, and A. L. Demirel, “Hydrogen-bonded multilayers of micelles of a dually responsive dicationic block copolymer,” SOFT MATTER, pp. 827–836, 2012, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/36223.