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- ItemModified bibenzimidazole ligands as spectator ligands in photoactive molecular functional Ru-polypyridine units? Implications from spectroscopy(Cambridge : RSC, 2014) Meyer-Ilse, J.; Bauroth, S.; Bräutigam, M.; Schmitt, M.; Popp, J.; Beckert, R.; Rockstroh, N.; Pilz, T.D.; Monczak, K.; Heinemann, F.W.; Rau, S.; Dietzek, B.The photophysical properties of Ruthenium-bipyridine complexes bearing a bibenzimidazole ligand were investigated. The nitrogens on the bibenzimidazole-ligand were protected, by adding either a phenylene group or a 1,2-ethandiyl group, to remove the photophysical dependence of the complex on the protonation state of the bibenzimidazole ligand. This protection results in the bibenzimidazole ligand contributing to the MLCT transition, which is experimentally evidenced by (resonance) Raman scattering in concert with DFT calculations for a detailed mode assignment in the (resonance) Raman spectra.
- ItemRuthenium(II)-bis(4'-(4-ethynylphenyl)-2,2':6', 2''-terpyridine) - A versatile synthon in supramolecular chemistry. Synthesis and characterization(Warsaw : Central European Science Journals, 2011) Siebert, R.; Schlütter, F.; Winter, A.; Presselt, M.; Görls, H.; Schubert, U.S.; Dietzek, B.; Popp, J.A homoleptic ethynyl-substituted ruthenium(II)-bisterpyridine complex representing a versatile synthon in supramolecular chemistry was synthesized and analyzed by NMR spectroscopy, mass spectrometry and X-ray diffractometry. Furthermore, its photophysical properties were detailed by UV/Vis absorption, emission and resonance Raman spectroscopy. In order to place the results obtained in the context of the vast family of ruthenium coordination compounds, two structurally related complexes were investigated accordingly. These reference compounds bear either no or an increased chromophore in the 4̀-position. The spectroscopic investigations reveal a systematic bathochromic shift of the absorption and emission maximum upon increasing chromophore size. This bathochromic shift of the steady state spectra occurs hand in hand with increasing resonance Raman intensities upon excitation of the metal-to-ligand charge-transfer transition. The latter feature is accompanied by an increased excitation delocalization over the chromophore in the 4̀-position of the terpyridine. Thus, the results presented allow for a detailed investigation of the electronic effects of the ethynyl substituent on the metal-to-ligand charge-transfer states in the synthon for click reactions leading to coordination polymers.
- ItemEvaluation of colloids and activation agents for determination of melamine using UV-SERS(Washington, DC : American Chemical Society, 2012) Kämmer, E.; Dörfer, T.; Csáki, A.; Schumacher, W.; Da Costa Filho, P.A.; Tarcea, N.; Fritzsche, W.; Rösch, P.; Schmitt, M.; Popp, J.UV-SERS measurements offer a great potential for environmental or food (detection of food contaminats) analytics. Here, the UV-SERS enhancement potential of various kinds of metal colloids, such as Pd, Pt, Au, Ag, Au-Ag core-shell, and Ag-Au core-shell with different shapes and sizes, were studied using melamine as a test molecule. The influence of different activation (KF, KCl, KBr, K 2SO 4) agents onto the SERS activity of the nanomaterials was investigated, showing that the combination of a particular nanoparticle with a special activation agent is extremely crucial for the observed SERS enhancement. In particular, the size dependence of spherical nanoparticles of one particular metal on the activator has been exploited. By doing so, it could be shown that the SERS enhancement increases or decreases for increasing or decreasing size of a nanoparticle, respectively. Overall, the presented results demonstrate the necessity to adjust the nanoparticle size and the activation agent for different experiments in order to achieve the best possible UV-SERS results.
- ItemLight-triggered CO release from nanoporous non-wovens(London [u.a.] : Royal Society of Chemistry, 2014) Bohlender, C.; Gläser, S.; Klein, M.; Weisser, J.; Thein, S.; Neugebauer, U.; Popp, J.; Wyrwa, R.; Schiller, A.The water insoluble and photoactive CO releasing molecule dimanganese decacarbonyl (CORM-1) has been non-covalently embedded into poly(l-lactide-co-d/ l-lactide) fibers via electrospinning to enable bioavailability and water accessibility of CORM-1. SEM images of the resulting hybrid non-wovens reveal a nanoporous fiber morphology. Slight CO release from the CORM-1 in the electrospinning process induces nanoporosity. IR spectra show the same set of carbonyl bands for the CORM-1 precursor and the non-woven. When the material was exposed to light (365-480 nm), CO release from the incorporated CORM-1 was measured via heterogeneous myoglobin assay, a portable CO electrode and an IR gas cuvette. The CO release rate was wavelength dependent. Irradiation at 365 nm resulted in four times faster release than at 480 nm. 3.4 μmol of CO per mg non-woven can be generated. Mouse fibroblast 3T3 cells were used to show that the hybrid material is non-toxic in the darkness and strongly photocytotoxic when light is applied.
- ItemHD DVD substrates for surface enhanced Raman spectroscopy analysis: fabrication, theoretical predictions and practical performance(London : RSC Publishing, 2016) Radu, A.I.; Ussembayev, Y.Y.; Jahn, M.; Schubert, U.S.; Weber, K.; Cialla-May, D.; Hoeppener, S.; Heisterkamp, A.; Popp, J.Commercial HD DVDs provide a characteristic structure of encoding pits which were utilized to fabricate cost efficiently large area SERS substrates for chemical analysis. The study targets the simulation of the plasmonic structure of the substrates and presents an easily accessible fabrication process to obtain highly sensitive SERS active substrates. The theoretical simulation predicted the formation of supermodes under optimized illumination conditions, which were verified experimentally. First tests of the developed SERS substrates demonstrated their excellent potential for detecting vitamin A and pro-vitamin A at low concentration levels.