@phdthesis{Mauser2006, author = {Mauser, Tatjana}, title = {Multilayer capsules with stimuli-sensitive properties : pH-response and carbohydrate-sensing}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12529}, school = {Universit{\"a}t Potsdam}, year = {2006}, abstract = {Polyelectrolyte microcapsules containing stimuli-responsive polymers have potential applications in the fields of sensors or actuators, stimulable microcontainers and controlled drug delivery. Such capsules were prepared, with the focus on pH-sensitivity and carbohydrate-sensing. First, pH-responsive polyelectrolyte capsules were produced by means of electrostatic layer-by-layer assembly of oppositely charged weak polyelectrolytes onto colloidal templates that were subsequently removed. The capsules were composed of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) or poly(4-vinylpyridine) (P4VP) and PMA and varied considerably in their hydrophobicity and the influence of secondary interactions. These polymers were assembled onto CaCO3 and SiO2 particles with diameters of ~ 5 µm, and a new method for the removal of the silica template under mild conditions was proposed. The pH-dependent stability of PAH/PMA and P4VP/PMA capsules was studied by confocal laser scanning microscopy (CLSM). They were stable over a wide pH-range and exhibited a pronounced swelling at the edges of stability, which was attributed to uncompensated positive or negative charges within the multilayers. The swollen state could be stabilized when the electrostatic repulsion was counteracted by hydrogen-bonding, hydrophobic interactions or polymeric entanglement. This stabilization made it possible to reversibly swell and shrink the capsules by tuning the pH of the solution. The pH-dependent ionization degree of PMA was used to modulate the binding of calcium ions. In addition to the pH-sensitivity, the stability and the swelling degree of these capsules at a given pH could be modified, when the ionic strength of the medium was altered. The reversible swelling was accompanied by reversible permeability changes for low and high molecular weight substances. The permeability for glucose was evaluated by studying the time-dependence of the buckling of the capsule walls in glucose solutions and the reversible permeability modulation was used for the encapsulation of polymeric material. A theoretical model was proposed to explain the pH-dependent size variations that took into account an osmotic expanding force and an elastic restoring force to evaluate the pH-dependent size changes of weak polyelectrolyte capsules. Second, sugar-sensitive multilayers were assembled using the reversible covalent ester formation between the polysaccharide mannan and phenylboronic acid moieties that were grafted onto poly(acrylic acid) (PAA). The resulting multilayer films were sensitive to several carbohydrates, showing the highest sensitivity to fructose. The response to carbohydrates resulted from the competitive binding of small molecular weight sugars and mannan to the boronic acid groups within the film, and was observed as a fast dissolution of the multilayers, when they were brought into contact with the sugar-containing solution above a critical concentration. It was also possible to prepare carbohydrate-sensitive multilayer capsules, and their sugar-dependent stability was investigated by following the release of encapsulated rhodamine-labeled bovine serum albumin (TRITC-BSA).}, language = {en} } @misc{DoscheMicklerLoehmannsroebenetal.2007, author = {Dosche, Carsten and Mickler, Wulfhard and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Agenet, Nicolas and Vollhardt, K. Peter C.}, title = {Photoinduced electron transfer in [N]phenylenes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12463}, year = {2007}, abstract = {First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.}, language = {en} } @misc{KumkeEidner2005, author = {Kumke, Michael Uwe and Eidner, Sascha}, title = {Fluorescence and energy transfer processes of humic substances and related model compounds in terbium complexes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12255}, year = {2005}, abstract = {The fluorescence properties and the fluorescence quenching by Tb3+ of substituted benzoic acid were investigated in solution at different pH. The substituted benzoic acids were used as simple model compounds for chromophores present in humic substances (HS). It is shown that the fluorescence properties of the model compounds resemble fluorescence of HS quite well. A major factor determining the fluorescence of model compounds are proton transfer reactions in the electronically excited state. It is intriguing that the fluorescence of the model compounds was almost not quenched by Tb3+ while the HS fluorescence was decreased very effectively. From our results we concluded that proton transfer reactions as well as conformational reorientation processes play an important role in the fluorescence of HS. The luminescence of bound Tb3+ was sensitized by an energy transfer step upon excitation of the model compounds and of HS, respectively. For HS the observed sensitization was dependent on its origin indicating differences 1) in the connection between chromophores and binding sites and 2) in the energy levels of the chromophore triplet states. Hence, the observed sensitization of the Tb3+ luminescence could be useful to characterize structural differences of HS in solution. Interlanthanide energy transfer between Tb3+ and Nd3+ was used to determine the average distance R between both ions using the well-known formalism of luminescence resonance energy transfer. R was dependent on the origin of the HS reflecting the difference in structure. The value of Rmin seemed to be a unique feature of the HS. It was further found that upon variation of the pH R also changed. This demonstrates that the measurement of interlanthanide energy transfer can be used as a direct method to monitor conformational changes in HS.}, language = {en} } @misc{EngelhardKumkeLoehmannsroeben2006, author = {Engelhard, Sonja and Kumke, Michael Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {OPQS - optical process and quality sensing : exemplary applications in the beerbrewing and polyurethane foaming processes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12191}, year = {2006}, abstract = {Optical methods play an important role in process analytical technologies (PAT). Four examples of optical process and quality sensing (OPQS) are presented, which are based on three important experimental techniques: near-infrared absorption, luminescence quenching, and a novel method, photon density wave (PDW) spectroscopy. These are used to evaluate four process and quality parameters related to beer brewing and polyurethane (PU) foaming processes: the ethanol content and the oxygen (O2) content in beer, the biomass in a bioreactor, and the cellular structures of PU foam produced in a pilot production plant.}, language = {en} } @misc{SchmaelzlinWalzKlimantetal.2006, author = {Schm{\"a}lzlin, Elmar and Walz, Bernd and Klimant, Ingo and Schewe, Bettina and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Monitoring hormone-induced oxygen consumption in the salivary glands of the blowfly, Calliphora vicina, by use of luminescent microbeads}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12206}, year = {2006}, abstract = {The salivary glands of the blowfly were injected with luminescent oxygen-sensitive microbeads. The changes in oxygen content within individual gland tubules during hormone-induced secretory activity were quantified. The measurements are based on an upgraded phase-modulation technique, where the phase shift of the sensor phosphorescence is determined independently from concentration and background signals. We show that the combination of a lock-in amplifier with a fluorescence microscope results in a convenient setup to measure oxygen concentrations within living animal tissues at the cellular level.}, language = {en} } @misc{HildebrandtCharbonniereZiesseletal.2006, author = {Hildebrandt, Nico and Charbonni{\`e}re, Lo{\"i}c J. and Ziessel, Raymond F. and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Quantum dots as resonance energy transfer acceptors for monitoring biological interactions}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12213}, year = {2006}, abstract = {Quantum dots (QDs) are common as luminescing markers for imaging in biological applications because their optical properties seem to be inert against their surrounding solvent. This, together with broad and strong absorption bands and intense, sharp tuneable luminescence bands, makes them interesting candidates for methods utilizing Forster Resonance Energy Transfer (FRET), e. g. for sensitive homogeneous fluoroimmunoassays (FIA). In this work we demonstrate energy transfer from Eu3+-trisbipyridin (Eu-TBP) donors to CdSe-ZnS-QD acceptors in solutions with and without serum. The QDs are commercially available CdSe-ZnS core-shell particles emitting at 655 nm (QD655). The FRET system was achieved by the binding of the streptavidin conjugated donors with the biotin conjugated acceptors. After excitation of Eu-TBP and as result of the energy transfer, the luminescence of the QD655 acceptors also showed lengthened decay times like the donors. The energy transfer efficiency, as calculated from the decay times of the bound and the unbound components, amounted to 37\%. The Forster-radius, estimated from the absorption and emission bands, was ca. 77{\AA}. The effective binding ratio, which not only depends on the ratio of binding pairs but also on unspecific binding, was obtained from the donor emission dependent on the concentration. As serum promotes unspecific binding, the overall FRET efficiency of the assay was reduced. We conclude that QDs are good substitutes for acceptors in FRET if combined with slow decay donors like Europium. The investigation of the influence of the serum provides guidance towards improving binding properties of QD assays.}, language = {en} } @misc{SchulerLipmanSteinbachetal.2005, author = {Schuler, Benjamin and Lipman, Everett A. and Steinbach, Peter J. and Kumke, Michael Uwe and Eaton, William A.}, title = {Polyproline and the "spectroscopic ruler" revisited with single-molecule fluorescence}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12229}, year = {2005}, abstract = {To determine whether F{\"o}rster resonance energy transfer (FRET) measurements can provide quantitative distance information in single-molecule fluorescence experiments on polypeptides, we measured FRET efficiency distributions for donor and acceptor dyes attached to the ends of freely diffusing polyproline molecules of various lengths. The observed mean FRET efficiencies agree with those determined from ensemble lifetime measurements but differ considerably from the values expected from F{\"o}rster theory, with polyproline treated as a rigid rod. At donor-acceptor distances much less than the F{\"o}rster radius R0, the observed efficiencies are lower than predicted, whereas at distances comparable to and greater than R0, they are much higher. Two possible contributions to the former are incomplete orientational averaging during the donor lifetime and, because of the large size of the dyes, breakdown of the point-dipole approximation assumed in F{\"o}rster theory. End-to-end distance distributions and correlation times obtained from Langevin molecular dynamics simulations suggest that the differences for the longer polyproline peptides can be explained by chain bending, which considerably shortens the donor-acceptor distances.}, language = {en} } @misc{SchmaelzlinDongenKlimantetal.2005, author = {Schm{\"a}lzlin, Elmar and Dongen, Joost T. van and Klimant, Ingo and Marmod{\´e}e, Bettina and Steup, Martin and Fishahn, Joachim and Geigenberger, Peter and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {An optical multifrequency phase-modulation method using microbeads for measuring intracellular oxygen concentrations in plants}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12232}, year = {2005}, abstract = {A technique has been developed to measure absolute intracellular oxygen concentrations in green plants. Oxygen-sensitive phosphorescent microbeads were injected into the cells and an optical multifrequency phase-modulation technique was used to discriminate the sensor signal from the strong autofluorescence of the plant tissue. The method was established using photosynthesis-competent cells of the giant algae Chara corallina L., and was validated by application to various cell types of other plant species.}, language = {en} } @misc{LemkeFernandezTrujilloLoehmannsroeben2005, author = {Lemke, Matthias and Fern{\´a}ndez-Trujillo, Rebeca and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {In-situ LIF analysis of biological and petroleum-based hydraulic oils on soil}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12268}, year = {2005}, abstract = {Absorption and fluorescence properties of 4 hydraulic oils (3 biological and 1 petroleum-based) were investigated. In-situ LIF (laser-induced fluorescence) analysis of the oils on a brown sandy loam soil was performed. With calibration, quantitative detection was achieved. Estimated limits of detection were below ca. 500 mg/kg for the petroleum-based oil and ca. 2000 mg/kg for one biological oil. A semi-quantitative classification scheme is proposed for monitoring of the biological oils. This approach was applied to investigate the migration of a biological oil in soil-containing compartments, namely a soil column and a soil bed.}, language = {en} } @misc{BillardAnsoborloAppersonetal.2003, author = {Billard, Isabelle and Ansoborlo, Eric and Apperson, Kathleen and Arpigny, Sylvie and Azenha, M. Emilia and Birch, David and Bros, Pascal and Burrows, Hugh D. and Choppin, Gregory and Kumke, Michael Uwe}, title = {Aqueous solutions of Uranium(VI) as studied by time-resolved emission spectroscopy : a Round-Robin Test}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12318}, year = {2003}, abstract = {Results of an inter-laboratory round-robin study of the application of time-resolved emission spectroscopy (TRES) to the speciation of uranium(VI) in aqueous media are presented. The round-robin study involved 13 independent laboratories, using various instrumentation and data analysis methods. Samples were prepared based on appropriate speciation diagrams and, in general, were found to be chemically stable for at least six months. Four different types of aqueous uranyl solutions were studied: (1) acidic medium where UO22+aq is the single emitting species, (2) uranyl in the presence of fluoride ions, (3) uranyl in the presence of sulfate ions, and (4) uranyl in aqueous solutions at different pH, promoting the formation of hydrolyzed species. Results between the laboratories are compared in terms of the number of decay components, luminescence lifetimes, and spectral band positions. The successes and limitations of TRES in uranyl analysis and speciation in aqueous solutions are discussed.}, language = {en} }