TY  - JOUR
A1  - Kopec, Maciej
A1  - Rozpedzik, Anna
A1  - Lapok, Lukasz
A1  - Geue, Thomas
A1  - Laschewsky, Andre
A1  - Zapotoczny, Szczepan
T1  - Stratified Micellar Multilayers-Toward Nanostructured Photoreactors
JF  - Chemistry of materials : a publication of the American Chemical Society
N2  - Polyelectrolyte multilayers (PEMs) with stratification of the internal structure were assembled from statistical amphiphilic copolyelectrolytes of opposite charges. These polyelectrolytes organize in aqueous solutions into micellar structures with fluoroalkyl and aromatic nanodomains, respectively, that were also preserved after deposition as thin films via layer-by-layer (LbL) electrostatic self-assembly. The unimolecular micelles, formed due to statistical compositions of amphiphilic polyelectrolytes used, were shown to suppress chain interdiffusion between adjacent layers in resulting micellar PEMs, as evidenced by spectroscopic ellipsometry, atomic force microscopy (AFM), and neutron reflectometry (NR) measurements. Additionally, hydrophobic cores of the micelles were used as hosts for photoactive molecules, namely, ferrocene and perfluorinated magnesium phthalocyanine. Stratified micellar multilayers were then deposited as hollow capsules using CaCO3 microparticles as templates. Photoinduced electron transfer (PET) between ferrocene and phthalocyanine solubilized in the polymer micelles was demonstrated to occur efficiently inside the stratified, polyelectrolyte walls of the capsules, due to the polarity gradient created by the incompatible aromatic and fluoroalkyl domains. The obtained results present a new approach to construct well-organized, self-assembled nanostructured materials for solar energy conversion.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.chemmater.6b00161
SN  - 0897-4756
SN  - 1520-5002
VL  - 28
SP  - 2219
EP  - 2228
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kopec, Maciej
A1  - Lapok, Lukasz
A1  - Laschewsky, André
A1  - Zapotoczny, Szczepan
A1  - Nowakowska, Maria
T1  - Polyelectrolyte multilayers with perfluorinated phthalocyanine selectively entrapped inside the perfluorinated nanocompartments
JF  - Soft matter
N2  - A novel perfluorinated magnesium phthalocyanine (MgPcF64) was synthesized and employed to probe nanodomains in hydrophobically modified, amphiphilic cationic polyelectrolytes bearing alkyl and/or fluoroalkyl side chains. MgPcF64 was found to be solubilized exclusively in the aqueous solutions of the fluorocarbon modified polycations, occupying the perfluorinated nanocompartments provided, while analogous polyelectrolytes with alkyl side chains forming hydrocarbon nanocompartments could not host the MgPcF64 dye. Multilayer films were fabricated by means of the layer-by-layer (LbL) deposition method using sodium poly(styrene sulfonate) as a polyanion. Linear multilayer growth was confirmed by UV-Vis spectroscopy and spectroscopic ellipsometry. Atomic force microscopy studies indicated that the micellar conformation of the polycations is preserved in the multilayer films. Fluorescence spectroscopy measurements confirmed that MgPcF64 stays embedded inside the fluorocarbon domains after the deposition process. This facile way of selectively incorporating water-insoluble, photoactive molecules into the structure of polyelectrolyte multilayers may be utilized for nanoengineering of ultrathin film-based optoelectronic devices.
Y1  - 2014
U6  - https://doi.org/10.1039/c2sm26938d
SN  - 1744-683X
SN  - 1744-6848
VL  - 10
IS  - 10
SP  - 1481
EP  - 1488
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  -