TY  - JOUR
A1  - Koc, Julian
A1  - Schardt, Lisa
A1  - Nolte, Kim
A1  - Beyer, Cindy
A1  - Eckhard, Till
A1  - Schwiderowski, Philipp
A1  - Clarke, Jessica L.
A1  - Finlay, John A.
A1  - Clare, Anthony S.
A1  - Muhler, Martin
A1  - Laschewsky, André
A1  - Rosenhahn, Axel
T1  - Effect of dipole orientation in mixed, charge-equilibrated self-assembled monolayers on protein adsorption and marine biofouling
JF  - ACS applied materials & interfaces
N2  - While zwitterionic interfaces are known for their excellent low-fouling properties, the underlying molecular principles are still under debate. In particular, the role of the zwitterion orientation at the interface has been discussed recently. For elucidation of the effect of this parameter, self-assembled monolayers (SAMs) on gold were prepared from stoichiometric mixtures of oppositely charged alkyl thiols bearing either a quaternary ammonium or a carboxylate moiety. The alkyl chain length of the cationic component (11-mercaptoundecyl)-N,N,N-trimethylammonium, which controls the distance of the positively charged end group from the substrate's surface, was kept constant. In contrast, the anionic component and, correspondingly, the distance of the negatively charged carboxylate groups from the surface was varied by changing the alkyl chain length in the thiol molecules from 7 (8-mercaptooctanoic acid) to 11 (12-mercaptododecanoic acid) to 15 (16-mercaptohexadecanoic acid). In this way, the charge neutrality of the coating was maintained, but the charged groups exposed at the interface to water were varied, and thus, the orientation of the dipoles in the SAMs was altered. In model biofouling studies, protein adsorption, diatom accumulation, and the settlement of zoospores were all affected by the altered charge distribution. This demonstrates the importance of the dipole orientation in mixed-charged SAMs for their inertness to nonspecific protein adsorption and the accumulation of marine organisms. Overall, biofouling was lowest when both the anionic and the cationic groups were placed at the same distance from the substrate's surface.
KW  - SAM
KW  - antifouling coatings
KW  - zwitterionic
KW  - XPS
KW  - Navicula perminuta
KW  - Ulva linza
KW  - SPR
Y1  - 2020
U6  - https://doi.org/10.1021/acsami.0c11580
SN  - 1944-8244
SN  - 1944-8252
VL  - 12
IS  - 45
SP  - 50953
EP  - 50961
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Schönemann, Eric
A1  - Koc, Julian
A1  - Karthäuser, Jana
A1  - Özcan, Onur
A1  - Schanzenbach, Dirk
A1  - Schardt, Lisa
A1  - Rosenhahn, Axel
A1  - Laschewsky, André
T1  - Sulfobetaine methacrylate polymers of unconventional polyzwitterion architecture and their antifouling properties
JF  - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences
N2  - Combining high hydrophilicity with charge neutrality, polyzwitterions are intensely explored for their high biocompatibility and low-fouling properties. Recent reports indicated that in addition to charge neutrality, the zwitterion's segmental dipole orientation is an important factor for interacting with the environment. Accordingly, a series of polysulfobetaines with a novel architecture was designed, in which the cationic and anionic groups of the zwitterionic moiety are placed at equal distances from the backbone. They were investigated by in vitro biofouling assays, covering proteins of different charges and model marine organisms. All polyzwitterion coatings reduced the fouling effectively compared to model polymer surfaces of poly(butyl methacrylate), with a nearly equally good performance as the reference polybetaine poly(3-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)propanesulfonate). The specific fouling resistance depended on the detailed chemical structure of the polyzwitterions. Still, while clearly affecting the performance, the precise dipole orientation of the sulfobetaine group in the polyzwitterions seems overall to be only of secondary importance for their antifouling behavior.
Y1  - 2021
U6  - https://doi.org/10.1021/acs.biomac.0c01705
SN  - 1525-7797
SN  - 1526-4602
VL  - 22
IS  - 4
SP  - 1494
EP  - 1508
PB  - American Chemical Society
CY  - Washington
ER  -