RESUMEN
The detection of analyte-binding events by receptors is drawing together the fields of Raman spectroscopy and supramolecular chemistry. This study is intended to facilitate this cohering by examining a model in the solution phase. The resonance Raman scattering (RRS) spectra of the complexation between tetrathiafulvalene (TTF) and cyclobis(paraquat-p-phenylene) (CBPQT(4+)) has been used as the model system to characterize the binding event of a host-guest system. RRS spectra are generated by excitation (lambda(exc) = 785 nm) within the lowest-energy charge-transfer (CT) transition (lambda(max) = 865 nm) of the TTF subsetCBPQT(4+) complex. The paired binding curves from the RRS and UV-vis-NIR titration data agrees with prior work, and a DeltaG of -5.7 +/- 0.6 kcal mol(-1) (MeCN, 298 K) was obtained for the complexation of TTF with CBPQT(4+). Computations on the complex and its components reproduce the energy shifts and resonance enhancements of the Raman band intensities, providing a basis to identify the structural and vibrational changes occurring upon complexation. The changes in bond lengths coincide with partial depopulation of a TTF-based HOMO and population of a CBPQT(4+)-based LUMO through CT mixing in the ground state of 0.46e(-). The structural changes upon complexation generally lead to lower wavenumber vibrations and to changes in the normal mode descriptions.
RESUMEN
Introduction of biofuels to the fuel matrix poses new questions and challenges. The present study investigates the microbiological stability of biodiesel blends in small scale microcosms. The study presents results from incubations of diesel-biodiesel blends with contaminated inoculation water collected from diesel storage tanks to ensure the presence of relevant fuel degrading bacteria. DAPI and qPCR analyses has subsequently shown an increased bacterial growth and activity in the microcosms containing biodiesel blends as the carbon source compared to those microcosms where neat fossil diesel made up the carbon source. Several anaerobic microorganisms have been identified after incubation. Presence of methanogens, sulfate-reducing bacteria and nitrate reducing bacteria has furthermore been confirmed by chemical analyses, supplemented by observations of methane formation in biodiesel incubations. The findings will contribute to the knowledge base for a safer introduction of biodiesel in the fuel matrix by employment of proper house-keeping and monitoring methods.