TY - JOUR A1 - Pavlenko, Elena S. A1 - Sander, Mathias A1 - Cui, Q. A1 - Bargheer, Matias T1 - Gold Nanorods Sense the Ultrafast Viscoelastic Deformation of Polymers upon Molecular Strain Actuation JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - On the basis of the layer-by-layer deposition of polyelectrolytes, we have designed hybrid nanolayer composites for integrated optoacoustic experiments. The femtosecond-laser-excitation of an Azo functionalized film launches nanoscale strain waves at GHz frequencies into a transparent polymer layer. Gold nanorods deposited on the surface sense the arrival of these hyper-sound-waves on the picosecond time scale via a modification of their longitudinal plasmon resonance. We simulated the strain waves using a simple linear masses-and-springs model, which yields good agreement with the observed time scales associated with the nanolayer thicknesses of the constituent materials. From systematic experiments with calibrated strain amplitudes we conclude that reversible viscoelastic deformations of the polyelectrolyte multilayers are triggered by ultrashort pressure transients of about 4 MPa. Our experiments show that strain-mediated interactions in nanoarchitectures composed of molecular photoswitches and plasmonic particles may be used to design new functionalities. The approach combines the highly flexible and cost-effective preparation of polyelectrolyte multilayers with ultrafast molecular strain actuation and plasmonic sensing. Although we use simple flat layered structures for demonstration, this new concept can be used for three-dimensional nanoassemblies with different functionalities. The ultrafast and reversible nature of the response is highly desirable, and the short wavelength associated with the high frequency of the hyper-sound-waves connecting photoactive molecules and nanoparticles inherently gives spectroscopic access to the nanoscale. High-frequency elastic moduli are derived from the ultrafast spectroscopy of the hypersonic response in polyelectrolyte multilayers. Y1 - 2016 U6 - https://doi.org/10.1021/acs.jpcc.6b06915 SN - 1932-7447 VL - 120 SP - 24957 EP - 24964 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mitzscherling, Steffen A1 - Cui, Q. A1 - Koopman, Wouter-Willem Adriaan A1 - Bargheer, Matias T1 - Dielectric function of two-phase colloid-polymer nanocomposite JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The plasmon resonance of metal nanoparticles determines their optical response in the visible spectral range. Many details such as the electronic properties of gold near the particle surface and the local environment of the particles influence the spectra. We show how the cheap but highly precise fabrication of composite nanolayers by spin-assisted layer-by-layer deposition of polyelectrolytes can be used to investigate the spectral response of gold nanospheres (GNS) and gold nanorods (GNR) in a self-consistent way, using the established Maxwell-Garnett effective medium (MGEM) theory beyond the limit of homogeneous media. We show that the dielectric function of gold nanoparticles differs from the bulk value and experimentally characterize the shape and the surrounding of the particles thoroughly by SEM, AFM and ellipsometry. Averaging the dielectric functions of the layered surrounding by an appropriate weighting with the electric field intensity yields excellent agreement for the spectra of several nanoparticles and nanorods with various cover-layer thicknesses. Y1 - 2015 U6 - https://doi.org/10.1039/c5cp04326c SN - 1463-9076 SN - 1463-9084 VL - 17 IS - 44 SP - 29465 EP - 29474 PB - Royal Society of Chemistry CY - Cambridge ER -