Refine
Year of publication
- 2018 (4) (remove)
Language
- English (4)
Is part of the Bibliography
- yes (4)
Keywords
- PNIPAm (1)
- UV cross-linking (1)
- atomic-force; nano-objects (1)
- azobenzene (1)
- azobenzene-containing molecules (1)
- brushes (1)
- chromophore orientations (1)
- elastomers (1)
- hydrogels (1)
- light responsive DNA (1)
Institute
- Institut für Physik und Astronomie (4) (remove)
We review recent progress in the field of light responsive soft nano-objects. These are systems the shape, size, surface area and surface energy of which can be easily changed by low-intensity external irradiation. Here we shall specifically focus on microgels, DNA molecules, polymer brushes and colloidal particles. One convenient way to render these objects photosensitive is to couple them via ionic and/or hydrophobic interactions with azobenzene containing surfactants in a non-covalent way. The advantage of this strategy is that these surfactants can make any type of charged object light responsive without the need for possibly complicated (and irreversible) chemical conjugation. In the following, we will exclusively discuss only photosensitive surfactant systems. These contain a charged head and a hydrophobic tail into which an azobenzene group is incorporated, which can undergo reversible photo-isomerization from a trans-to a cis-configuration under UV illumination. These kinds of photo-isomerizations occur on a picosecond timescale and are fully reversible. The two isomers in general possess different polarity, i.e. the trans-state is less polar with a dipole moment of usually close to 0 Debye, while the cis-isomer has a dipole moment up to 3 Debye or more, depending on additional phenyl ring substituents. As part of the hydrophobic tail of a surfactant molecule, the photo-isomerization also changes the hydrophobicity of the molecule as a whole and hence its solubility, surface energy, and strength of interaction with other substances. Being a molecular actuator, which converts optical energy in to mechanical work, the azobenzene group in the shape of surfactant molecule can be utilized in order to actuate matter on larger time and length scale. In this paper we show several interesting examples, where azobenzene containing surfactants play the role of a transducer mediating between different states of size, shape, surface energy and spatial arrangement of various nanoscale soft-material systems.
We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 mu m in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [J. Phys. Chem. Lett. 2017, 8, 1094], we calculated the optomechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results.
We report on the formation of stimuli-responsive structured hydrogel thin films whose pattern geometry can be adjusted on demand and tuned reversibly by varying solvent quality or by changing temperature. The hydrogel films, similar to 100 nm in thickness, were prepared by depositing layers of random copolymers comprising N-isopropylacrylamide and ultraviolet (UV)-active methacryloyloxybenzophenone units onto solid substrates. A two-beam interference pattern technique was used to cross-link the selected areas of the film; any unreacted material was extracted using ethanol after UV light-assisted cross-linking. In this way, we produced nanoholes, perfectly ordered structures with a narrow size distribution, negligible tortuosity, adjustable periodicity, and a high density. The diameter of the circular holes ranged from a few micrometers down to several tens of nanometers; the hole periodicity could be adjusted readily by changing the optical period of the UV interference pattern. The holes were reversibly closed and opened by swelling/deswelling the polymer networks in the presence of ethanol and water, respectively, at various temperatures. The reversible regulation of the hole diameter can be repeated many times within a few seconds. The hydrogel sheet with circular holes periodically arranged may also be transferred onto different substrates and be employed as tunable templates for the deposition of desired substances.
In this paper two groups supporting different views on the mechanism of light induced polymer deformation argue about the respective underlying theoretical conceptions, in order to bring this interesting debate to the attention of the scientific community. The group of Prof. Nicolae Hurduc supports the model claiming that the cyclic isomerization of azobenzenes may cause an athermal transition of the glassy azobenzene containing polymer into a fluid state, the so-called photo-fluidization concept. This concept is quite convenient for an intuitive understanding of the deformation process as an anisotropic flow of the polymer material. The group of Prof. Svetlana Santer supports the re-orientational model where the mass-transport of the polymer material accomplished during polymer deformation is stated to be generated by the light-induced re-orientation of the azobenzene side chains and as a consequence of the polymer backbone that in turn results in local mechanical stress, which is enough to irreversibly deform an azobenzene containing material even in the glassy state. For the debate we chose three polymers differing in the glass transition temperature, 32 °C, 87 °C and 95 °C, representing extreme cases of flexible and rigid materials. Polymer film deformation occurring during irradiation with different interference patterns is recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. We also demonstrated the unique behaviour of azobenzene containing polymeric films to switch the topography in situ and reversibly by changing the irradiation conditions. We discuss the results of reversible deformation of three polymers induced by irradiation with intensity (IIP) and polarization (PIP) interference patterns, and the light of homogeneous intensity in terms of two approaches: the re-orientational and the photo-fluidization concepts. Both agree in that the formation of opto-mechanically induced stresses is a necessary prerequisite for the process of deformation. Using this argument, the deformation process can be characterized either as a flow or mass transport.