Light-triggered polymer diffusion in anisotropic multizone films
Final Report Abstract
This project demonstrates the development of NIR-light responsive soft planar structures serving as light-triggered reservoirs for remotely controlled molecular transport. Systems of biopolymer-based multilayers (hyaluronan/polylysine) n coated by a compact layer of Poly-N-isopropylacrylamide (PNIPAM) microgels doped with gold nanorods have been assembled and analysed for the first time. The gold particles were successfully and long term-attached to the PNIPAM microgels. Thermoresponsive behaviour of the immobilized microgels and those in solution show a reversible microgel shrinkage at temperatures above the lower critical solution temperature (ca. 32oC). A dynamic light scattering (DLS) based setup has been developed for real time monitoring of light-mediated shrinkage of the hybrid microgels. Therefore, a second laser was coupled into the DLS se-up for plasmon excitation at the gold nanoparticles. It serves as a unique tool for understanding of behaviour of temperature sensitive polymers in confined volumes. Further we have developed a new approach for the analysis of molecular diffusion inside multilayers with emphasis on the diffusion of multiple populations of molecules. This helped to decipher the mechanisms of protein diffusion inside multilayers as well as to analyse loading and retention of molecules in multilayers. NIR-light triggered enhancement of release of dextran-FITC loaded into the systems of multilayers capped with hybrid microgels can be reversible, demonstrating the proof of concept of the externally triggered gating function. The mechanism of release and stability of the PEM/hybrid layers upon NIR- light irradiation are addressed based on morphological analysis at various irradiation conditions. The approach developed for light-triggered molecular transport shows attractive perspectives for development of extracellular matrix (ECM) mimics which offer a high level of external control over chemical cues in space and time. Since multilayers belong to one of the best ECM mimics due to finely tuneable compositions and physical-chemical properties, it is indispensable for biological applications to exploit them in order to achieve a better understanding of the ECM signal dynamics. Optimization of the PEM/hybrid layers developed will allow us in the future to tune molecular transport and therefore adjust presentation of bioactive molecules with a high precision in space and time. This makes the approach developed superior and especially attractive for biological applications because of the non-invasive nature of the NIR-light and unique opportunities to adjust modes of the application of light (focusing, intensity variation, etc).
Publications
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“3d localization and diffusion of proteins in polyelectrolyte multilayers.”Soft Matter 2012, 8, 11786
Uhlig, K.; Madaboosi, N.; Schmidt, S.; Jager, M. S.; Rose, J.; Duschl, C.; Volodkin, D. V.
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“Growth behaviour and mechanical properties of PLL/HA multilayer films studied by AFM.”Beilstein J. Nanotechnol. 2012, 3, 778
Üzüm, C.; Hellweg, J.; Madaboosi, N.; Volodkin, D. V.; von Klitzing, R.
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“Microfluidics as A Tool to Understand the Build-Up Mechanism of Exponential-Like Growing Films.”Macromolecular Rapid Communications 2012, 33, 1775
Madaboosi, N.; Uhlig, K.; Jäger, M. S.; Möhwald, H.; Duschl, C.; Volodkin, D. V.
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“Interaction of gold nanoparticles with thermoresponsive microgels: influence of the cross-linker density on optical properties”. PCCP 2013, 15, 15623
Gawlitza, K.; Turner, S. T.; Polzer, F.; Wellert, S.; Karg, M.; Mulvaney, P.; von Klitzing, R
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”Temperature-induced molecular transport through polymer multilayers coated with PNIPAM microgels”. PCCP 2015, 17 12771
Vikulina, A.S.; Aleed, S.T.; Paulraj, T.; Vladimirov, Y.A.; Duschl, C. von Klitzing, R; Volodkin, D.V.
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“Mobility of Lysozyme in Poly(L-lysine)/Hyaluronic Acid Multilayer Films”. Colloids Surfaces B: Biointerfaces, 2016, 147, 343-350
Velk, N.; Uhlig, K.; Vikulina, A. S.; Duschl, C.; Volodkin, D.
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“Temperature effect on build-up of exponentially growing polyelectrolyte multilayers. Exponential-to-linear transition point'', PCCP 2016, 18, 7866
Vikulina, A.S.; Anissimov, Y.; Prokopovi, V.; Uhlig, K; Jaeger, M; von Klitzing, R.; Duschl, C.; Volodkin, D.V.
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“Communication: Light driven remote control of microgels’ size in the presence of photosensitive surfactant: Complete phase diagram'', J. Chem. Phys., 2017, 147, 031101
Schimka, S. Y., Gordievskaya, D.; Lomadze, N.; Lehmann, M.; von Klitzing, R.; Rumyantsev, A.M.; Kramarenko, E.; Santer, S.
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“A DLS Setup for In-Situ Measurements of Photo-Induced Size Changes of Microgel-based Hybrid Particles”, Langmuir, 2018, 34, 3597
Lehmann, M.; Tabaka, W.; Möller, T.; Oppermann, A.; Wöll, D.; Volodkin, D.; Wellert, S.; von Klitzing, R.
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“Multi-Fractional Analysis of Molecular Diffusion in Polymer Multilayers by FRAP. A New Simulation-Based Approach.” J Phys Chem B, 2018, 122, 1323
Sustr, D; Hlavacek, A; Duschl, C.; Volodkin, D.
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“Nanomechanics and Nanorheology of Microgels at Interfaces'', Polymers, 2018, 10, 978
Backes, S.; von Klitzing, R.
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“Cooling- Triggered Release from MesoporousPoly(N--isopropylacrylamide) Microgels at Physiological Conditions” ACS Appl. Mater. Interfaces 2020, 12, 57401
Vikulina, A.S.; Feoktistova, N.A.; Balabushevich, N.G.; von Klitzing, R.; Volodkin, D.
