No abstract

The supramolecular assembly of photoactive azobenzenes with passive polymers via halogen or hydrogen bonding is a cost-effective way to design materials for various photomechanical applications that convert light energy directly into macroscopic motion, for instance, in all-optical surface patterning and photochemical imaging of plasmonic structures. To elucidate the molecular-level origins of this motion, we show, by coupling dynamic infrared spectroscopy to a photo-orientation setup, that supramolecular bonds above a certain interaction strength threshold are photostable under vigorous photoisomerization cycling and capable of translating the photo-orientation of azobenzenes into the orientation of nonabsorbing host polymer side chains. A correlation is found between azobenzene photoinduced molecular orientation and macroscopic all-optical surface patterning efficiency. The improved performance of halogen-bonded systems in photopatterning applications can be related to the absence of a plasticizing effect on the polymer matrix, which may enable the material to retain an optimal glass transition temperature, in contrast to hydrogen-bonded and nonbonded references. Thus, our results provide design guidelines in terms of the nature and strength of the supramolecular interaction and of the degree of azo functionalization needed to optimize the motion transfer to passive polymers

We present an original, low-cost nanoplasmonic (bio)sensor based on crossed surface relief gratings (CSRGs) generated from orthogonally superimposed surface relief gratings (SRGs) on gold-coated azo-glass substrate. This surface plasmon resonance (SPR)-based sensing approach is unique, since the light transmitted through a CSRG is zero except in the narrow bandwidth where the SPR conversion occurs, enabling quantitative monitoring of only the plasmonic signal from biomolecular interactions in real time. We validated the individual SRG plasmonic signature of CSRGs by observing their respective SPR excitation peaks, and tested them to detect both bulk and near-surface refractive index (RI) changes. Compared to simple SRGs, CSRGs portray a much-improved sensitivity of 647.8 nm/RIU, a resolution on the order of 10 RIU, and a figure of merit (FOM) of 14 for bulk RI-change sensing. We also demonstrate their ability to perform as biosensors, through the detection and monitoring of near-surface biomolecular interactions in real time, a first for CSRGs. The minimum detectable concentration of biotin-streptavidin binding events was 8.3 nM. Due to their sensing abilities, low cost (<10 cents/unit), ease of fabrication, and inherent suitability for integration with microfluidics, we anticipate that CSRGs will stand as strong candidates in the portable diagnostics arena.

We have used resonance methods to determine the variation of all the independent piezoelectric, elastic, and dielectric material coefficients, as well as the corresponding electromechanical coupling factors, of soft and hard doped piezoelectric lead zirconate titanate (PZT) ceramics with compositions near the morphotropic phase boundary, as a function of temperature ranging between −165 and 195°C. The material coefficients were obtained by analyzing the fundamental resonance of the impedance or admittance spectra as a function of frequency for several sample resonance geometries. The piezoelectric coefficients d33, −d31, and d15, as well as the dielectric permittivity coefficients ε11T and ε33T, generally increased with temperature for both soft and hard PZT samples. However, the elastic compliance coefficients s11E, −s12E, s33E, and s55E exhibited abnormal variations seen as broad peaks over parts of the tested temperature range. Additionally, thermal hystereses were observed in all the studied material coefficients over the temperature cycle. Finally, it was noted that, overall, the material coefficients of soft PZT varied significantly more than those of hard PZT under changing temperature conditions.

The influence of the supramolecular interaction typehydrogen bonding, proton transfer, and pure ionic bondingon photoresponsive behavior, particularly surface relief grating (SRG) inscription, has been investigated using a homopolymer with an ambient temperature glass transition (T g ). To this end, poly(dimethylaminoethyl methacrylate) (PDMAEMA or PDM) of relatively high molecular weight (42K) was complexed at various azo/DM molar ratios with dimethylaminoazobenzene derivatives functionalized by hydroxyl (azoOH) or carboxylic acid (p-methyl red or azoCOOH) groups, and quaternized PDM (PDMQ) was complexed at equimolar ratio with a sulfonated analogue (methyl orange or azoSO 3 ), and the structural and thermal properties of these complexes were determined. SRG inscription on spin-coated films was found to be possible because complexation increases the T g above ambient. The efficiency of SRG inscription on spin-coated films, which increases with azo content, is highest for the purely ionic azoSO 3 /PDMQ complex despite its very high T g , while the proton transfer azoCOOH/ PDM complexes, involving ionic and H-bonding with acid-salt structures, show somewhat more efficient SRG inscription than do the purely hydrogen-bonded azoOH/PDM complexes, and this despite some azoCOOH crystallization at the highest molar ratios. These findings clarify the comparative effectiveness of different supramolecular bond types on SRG inscription and provide a useful guide for the design of supramolecular photoresponsive polymers for SRG applications.