Chemistry and Physics of Surfaces and Biointerfaces

The department of Chemistry and Physics of Surfaces and Biointerfaces focuses on developing new concepts in synthesis of smart bioresponsive polymer surfaces, with defined physico-chemical properties and known state of incorporated bioactive groups. The emerging polymer chemistry, surface engineering and biofunctionalization concepts strive to outperform the contemporary polymer surfaces used as biomaterials, scaffolds, sensors and micro-array assays. The team comprises members with multidisciplinary background, covering organic, polymer, physical and analytical chemistry, chemical engineering, biophysics, biochemistry and biotechnology. The interdisciplinary projects are formulated to fully address the chemistry and physics of various surfaces and biointerfaces, as well as to explain and control the complex surface/environment interactions and surface related phenomena.

Research scope

Macromolecular/polymer chemistry and biofunctionalization aspects

We utilize new types of controlled polymerizations and post-polymerization reactions enabling orthogonal conjugation to synthesize new biomedically relevant polymer surfaces with finely tuned architecture and functionality. Our research focusses on:

• controlled polymerizations of monomers relevant for tissue engineering, biosensing and biomedical applications;
• optimization of orthogonal reactions to synthesize different polymer surface architectures and patterns;
• biofunctionalization of the synthesized platforms with various biorecognition and bioactive molecules (including libraries of ECM-, hormone- and cadherin- derived peptides);
• self-assembly processes in bioinspired and biomimetic polymer systems.

 

Photoinduced single-electron transfer living
radical polymerization for the creation of
well-defined micropaterns of non-fouling
polymer brushes.

 

 

 

Applied physico-chemical aspects

The research addresses the physico-chemical aspects of surfaces and interfaces, the covalent and conformational state of the end-tethered polymer chains, the surface concentration, distribution and availability of the various groups (neutral, reactive and bioactive) present on the polymer surfaces, etc. For these purposes, we utilize surface-sensitive methods, such as spectroscopic ellipsometry, quartz crystal microbalance with dissipation monitoring, reflection modes of FTIR (such as ATR, RAS and GAATR), FT-Raman, and X-ray photoelectron spectroscopies, contact angle goniometry, atomic force microscopy (AFM) and radio-assay techniques. Near-field nano-FTIR and Tip-Enhanced Raman spectroscopies, as well as scattering-type scanning near-field optical microscopy are used for the nanoscale characterization of the brushes. Visualization, mapping and probing of the strength between the bioactive surface immobilized molecules and its counterparts is accomplished by single-molecule and single-cell force AFM-based spectroscopies.

     

The conformation and average orientation of chains
constituing few-nanometer-thin polymer brush layer
are extracted from measured mid-infrared nanoscopy
spectra with the aid of theoretic modelling, confirming
the spontaneous formation of crystalline and
amorphous phases.

 

 

Interactions with biological environment

Functional interfaces for bio-sensing applications are prepared through controlled covalent immobilization of biologically active molecules, such as specific antibodies, oligonucleotides and bioreceptor molecules to non-fouling surfaces of polymer brushes. The performed biosensors are successfully used for analysis of biomolecular interactions and diagnosis in clinical samples.

 

Antifouling polymer brushes prevent
detrimental biological processes
such as platelet adhesion and
activation leading to thrombosis.

 

 

 

Concept of macroporous PLCL capsules pre-
vascularized in greater omentum for subsequent
islets transplantation. The surface of the
channel-shaped pores of the capsule wall is
coated with LbL films releasing FGF-2/VEGF
growth factors, which promote the capsule
revascularization. The β-cells (brown) of the
transplanted islets produce insulin at
least 50 days after transplantation.

 

Representative results – Publications

1. de los Santos Pereira, A.; Cesnescu, A.; Svoboda, J.; Sivkova, R.; Romanenko, I.; Bashta, B.; Keilmann, F.; Pop-Georgievski, O., Conformation in Ultrathin Polymer Brush Coatings Resolved by Infrared Nanoscopy. Analytical Chemistry 2020, 92 (7), 4716—4720.
2. Kasoju, N.; Pátíková, A.; Wawrzynska, E.; Vojtíšková, A.; Sedlačík, T.; Kumorek, M.; Pop-Georgievski, O.; Sticová, E.; Kříž, J.; Kubies D., Bioengineering a pre-vascularized pouch for subsequent islet transplantation using VEGF-loaded polylactide capsules. Biomaterials Science 2020, 8 (2), 631—647.
3. Vorobii, M.; de los Santos Pereira, A.; Pop-Georgievski, O.; Kostina, N. Y.; Rodriguez-Emmenegger, C.; Percec, V., Synthesis of non-fouling poly[N-(2-hydroxypropyl)-methacrylamide] brushes by photoinduced SET-LRP. Polymer Chemistry 2015, 6 (23), 4210—4220.
4. de los Santos Pereira, A.; Sheikh, S.; Blaszykowski, C.; Pop-Georgievski, O.; Fedorov, K.; Thompson, M.; Rodriguez-Emmenegger, C., Antifouling Polymer Brushes Displaying Antithrombogenic Surface Properties. Biomacromolecules 2016, 17 (3), 1179—1185.
5. Riedel, T.; Surman, F.; Hageneder, S.; Pop-Georgievski, O.; Noehammer, C.; Hofner, M.; Brynda, E.; Rodriguez-Emmenegger, C.; Dostalek, J., Hepatitis B plasmonic biosensor for the analysis of clinical serum samples. Biosensors and Bioelectronics 2016, 85, 272—279.
6. Riedel, T.; Hageneder, S.; Surman, F.; Pop-Georgievski, O.; Noehammer, C.; Hofner, M.; Brynda, E.; Rodriguez-Emmenegger, C.; Dostalek, J., Plasmonic Hepatitis B Biosensor for the Analysis of Clinical Saliva. Analytical Chemistry 2017, 89 (5), 2972—2977.
7. Svoboda, J.; Sedlacek, O.; Riedel, T.; Hruby, M.; Pop-Georgievski, O., Poly(2-oxazoline)s One-Pot Polymerization and Surface Coating: From Synthesis to Antifouling Properties Out-Performing Poly(ethylene oxide). Biomacromolecules 2019, 20 (9), 3453—3463.

Cooperation

• Christopher Barner-Kowollik, Queensland University of Technology (Brisbane, Australia) and Karlsruhe Institute of Technology (Karlsruhe, Germany)
• Virgil Percec, University of Pennsylvania, Philadelphia, USA
• Cesar Rodriguez-Emmenegger, Leibniz Institute for Interactive Materials, Aachen, Germany
• Carsten Werner, Leibnitz Institute for Polymer Research, Dresden, Germany
• Michael Thompson, University of Toronto, Toronto, Canada
• Jakub Dostalek, Austrian Institute of Technology GmbH, Vienna, Austria
• Fritz Keilmann, Faculty of Physics, Ludwig-Maximilians-University, Munich, Germany
• Jiří Homola, Institute of Photonics and Electronics, Czech Academy of Sciences, Prague, Czech Republic
• Jakub Holovský, Centre for Advanced Photovoltaics, Faculty of Electrical Engineering, Czech Technical University in Prague, Prague, Czech Republic
• Lucie Bačáková, Institute of Physiology, Czech Academy of Sciences, Prague, Czech Republic

Funding support

• Unraveling the physicochemical phenomena leading to antifouling bioactive surfaces (C. Rodriguez-Emmenegger/O. Pop-Georgievski, Czech Science Foundation (CSF), 15-09368)
• Self-endothelialization of novel bioactive surfaces of decellularized vascular grafts (T. Riedel, CSF, GA18-01163S)
• Advanced plasmonic biosensors: towards the next-generation biomolecular interaction analysis (T. Riedel, CSF, GA19-02739S)
• Blood plasma individual variability and pathophysiology and their influence on the interactions with synthetic antifouling surfaces (T. Riedel, CSF, GA20-10845S)
• Study of the initial self-assembly processes during the formation of biomimetic anchor layers (J. Svoboda, CSF, GA20-08679S)
• Understanding the "whispers" at interfaces of bioactive polymer brushes (O. Pop-Georgievski, CSF, GA20-07313S)