@article{13386, abstract = {Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans–cis photoisomerization when diluted with alkanethiol spacers. Using these mixed SAMs, we show switching of the linear optical and second-harmonic response. The effective switching of these surface optical properties relies on a reasonably large cross section and a high photoisomerization yield as well as a long lifetime of the metastable cis isomer. We quantified the switching process by X-ray absorption spectroscopy. The cross sections for the trans–cis and cis–trans photoisomerization with 365 and 455 nm light, respectively, are 1 order of magnitude smaller than in solution. In vacuum, the 365 nm photostationary state comprises 50–74% of the molecules in the cis form, limited by their rapid thermal isomerization back to the trans state. In contrast, the 455 nm photostationary state contains nearly 100% trans-azobenzene. We determined time constants for the thermal cis–trans isomerization of only a few minutes in vacuum and in a dry nitrogen atmosphere but of more than 1 day in ambient air. Our results suggest that adventitious water adsorbed on the surface of the SAM stabilizes the polar cis configuration of azobenzene under ambient conditions. The back reaction rate constants differing by 2 orders of magnitude underline the huge influence of the environment and, accordingly, its importance when comparing various experiments.}, author = {Moldt, Thomas and Przyrembel, Daniel and Schulze, Michael and Bronsch, Wibke and Boie, Larissa and Brete, Daniel and Gahl, Cornelius and Klajn, Rafal and Tegeder, Petra and Weinelt, Martin}, issn = {1520-5827}, journal = {Langmuir}, keywords = {Electrochemistry, Spectroscopy, Surfaces and Interfaces, Condensed Matter Physics, General Materials Science}, number = {42}, pages = {10795--10801}, publisher = {American Chemical Society}, title = {{Differing isomerization kinetics of azobenzene-functionalized self-assembled monolayers in ambient air and in vacuum}}, doi = {10.1021/acs.langmuir.6b01690}, volume = {32}, year = {2016}, } @article{13396, abstract = {Photoswitching in densely packed azobenzene self-assembled monolayers (SAMs) is strongly affected by steric constraints and excitonic coupling between neighboring chromophores. Therefore, control of the chromophore density is essential for enhancing and manipulating the photoisomerization yield. We systematically compare two methods to achieve this goal: First, we assemble monocomponent azobenzene–alkanethiolate SAMs on gold nanoparticles of varying size. Second, we form mixed SAMs of azobenzene–alkanethiolates and “dummy” alkanethiolates on planar substrates. Both methods lead to a gradual decrease of the chromophore density and enable efficient photoswitching with low-power light sources. X-ray spectroscopy reveals that coadsorption from solution yields mixtures with tunable composition. The orientation of the chromophores with respect to the surface normal changes from a tilted to an upright position with increasing azobenzene density. For both systems, optical spectroscopy reveals a pronounced excitonic shift that increases with the chromophore density. In spite of exciting the optical transition of the monomer, the main spectral change in mixed SAMs occurs in the excitonic band. In addition, the photoisomerization yield decreases only slightly by increasing the azobenzene–alkanethiolate density, and we observed photoswitching even with minor dilutions. Unlike in solution, azobenzene in the planar SAM can be switched back almost completely by optical excitation from the cis to the original trans state within a short time scale. These observations indicate cooperativity in the photoswitching process of mixed SAMs.}, author = {Moldt, Thomas and Brete, Daniel and Przyrembel, Daniel and Das, Sanjib and Goldman, Joel R. and Kundu, Pintu K. and Gahl, Cornelius and Klajn, Rafal and Weinelt, Martin}, issn = {1520-5827}, journal = {Langmuir}, keywords = {Electrochemistry, Spectroscopy, Surfaces and Interfaces, Condensed Matter Physics, General Materials Science}, number = {3}, pages = {1048--1057}, publisher = {American Chemical Society}, title = {{Tailoring the properties of surface-immobilized azobenzenes by monolayer dilution and surface curvature}}, doi = {10.1021/la504291n}, volume = {31}, year = {2015}, } @article{13426, abstract = {Photoswelling of thin films of dichromated gelatin provides a basis for fabrication of multilevel surface reliefs via sequential UV illumination through different photomasks. The remarkable feature of this simple, benchtop technique is that by adjusting irradiation times, film thickness, or its hydration state the heights of the developed features can be varied from few nanometers to tens of microns. After UV exposure, the surface structures can be replicated faithfully into either soft or hard PDMS stamps.}, author = {Paszewski, Maciej and Smoukov, Stoyan K. and Klajn, Rafal and Grzybowski, Bartosz A.}, issn = {1520-5827}, journal = {Langmuir}, keywords = {Electrochemistry, Spectroscopy, Surfaces and Interfaces, Condensed Matter Physics, General Materials Science}, number = {10}, pages = {5419--5422}, publisher = {American Chemical Society}, title = {{Multilevel surface nano- and microstructuring via sequential photoswelling of dichromated gelatin}}, doi = {10.1021/la062982c}, volume = {23}, year = {2007}, } @article{13432, abstract = {A new experimental technique is described that uses reaction−diffusion phenomena as a means of one-step microfabrication of complex, multilevel surface reliefs. Thin films of dry gelatin doped with potassium hexacyanoferrate are chemically micropatterned with a solution of silver nitrate delivered from an agarose stamp. Precipitation reaction between the two salts causes the surface to deform. The mechanism of surface deformation is shown to involve a sequence of reactions, diffusion, and gel swelling/contraction. This mechanism is established experimentally and provides a basis of a theoretical lattice-gas model that allows prediction surface topographies emerging from arbitrary geometries of the stamped features. The usefulness of the technique is demonstrated by using it to rapidly prepare two types of mold for passive microfluidic mixers.}, author = {Campbell, Christopher J. and Klajn, Rafal and Fialkowski, Marcin and Grzybowski, Bartosz A.}, issn = {1520-5827}, journal = {Langmuir}, keywords = {Electrochemistry, Spectroscopy, Surfaces and Interfaces, Condensed Matter Physics, General Materials Science}, number = {1}, pages = {418--423}, publisher = {American Chemical Society}, title = {{One-step multilevel microfabrication by reaction−diffusion}}, doi = {10.1021/la0487747}, volume = {21}, year = {2005}, }