Polybetaine nanobrushes are widely used as inert platforms for label-free biosensing due to their resistance to nonspecific interactions. Despite being considered cationic or electrically neutral, polybetaines can exhibit a negative zeta potential (ZP) at pHs above their isoelectric point (pI). To clarify whether negative zeta potential effectively contributes to surface interactions, we examined three types of nanobrushes deposited on a planar gold substrate: two polybetaines: poly(carboxybetaine methacrylamide) (pCBMAA) and poly(sulfobetaine methacrylamide) (pSBMAA) and hydrophilic poly[N-(2-hydroxypropyl) methacrylamide] (pHPMAA), which carries no ionic group. All three brushes exhibit a well-defined pI and negative surface ZP at pHs above their pI. The pH dependence of the interactions of these brushes with anionic dextran sulfate (DS) and cationic poly[(N-trimethylammonium)ethyl methacrylate] (PTMAEMA) was monitored by infrared reflection spectroscopies (infrared reflection absorption spectroscopy (IRRAS), grazing angle attenuated total reflectance (GAATR)). DS adsorbs to pCBMAA strongly and only weakly to pSBMAA at pHs below their pI but can adsorb slightly to both polybetaines even at pHs above their pI. This is due to the displacement of their carboxylate or sulfo groups from the interaction with the quaternary ammonium cation by the DS sulfate groups. However, DS does not adsorb to pHPMAA at any pH, and PTMAEMA does not adsorb to any of the brushes, regardless of pH. These findings highlight that zeta potential determinations alone may not be sufficient to predict electrostatic interactions as the apparent negative charge does not necessarily translate into a functional surface charge influencing macromolecular interactions.

• Publikační typ
• časopisecké články MeSH

Cells are continuously sensing their microenvironment and subsequently respond to different physicochemical cues by the activation or inhibition of different signaling pathways. To study a very complex cellular response, it is necessary to diminish background environmental influences and highlight the particular event. However, surface-driven nonspecific interactions of the abundant biomolecules from the environment influence the targeted cell response significantly. Yes-associated protein (YAP) translocation may serve as a marker of human hepatocellular carcinoma (Huh7) cell responses to the extracellular matrix and surface-mediated stresses. Here, we propose a platform of tunable functionable antifouling poly(carboxybetain) (pCB)-based brushes to achieve a molecularly clean background for studying arginine, glycine, and aspartic acid (RGD)-induced YAP-connected mechanotransduction. Using two different sets of RGD-functionalized zwitterionic antifouling coatings with varying compositions of the antifouling layer, a clear correlation of YAP distribution with RGD functionalization concentrations was observed. On the other hand, commonly used surface passivation by the oligo(ethylene glycol)-based self-assembled monolayer (SAM) shows no potential to induce dependency of the YAP distribution on RGD concentrations. The results indicate that the antifouling background is a crucial component of surface-based cellular response studies, and pCB-based zwitterionic antifouling brush architectures may serve as a potential next-generation easily functionable surface platform for the monitoring and quantification of cellular processes.

• Klíčová slova
• antifouling polymer brushes, cell mechanotransduction, cell signaling, functional biointerfaces, surface modification, zwitterionic material,
• MeSH
• akrylamidy chemie   MeSH
• biokompatibilní potahované materiály chemie   MeSH
• bioznečištění prevence a kontrola   MeSH
• buněčný převod mechanických signálů * MeSH
• extracelulární matrix metabolismus   MeSH
• lidé MeSH
• mechanický stres MeSH
• nádorové buněčné linie MeSH
• oligopeptidy chemie   MeSH
• protoonkogenní proteiny c-yes metabolismus   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• akrylamidy MeSH
• arginyl-glycyl-aspartic acid MeSH Prohlížeč
• biokompatibilní potahované materiály MeSH
• oligopeptidy MeSH
• protoonkogenní proteiny c-yes MeSH
• YES1 protein, human MeSH Prohlížeč
• zwitterion carboxybetaine acrylamide MeSH Prohlížeč