@misc{KumkeKlier2015, author = {Kumke, Michael Uwe and Klier, Dennis Tobias}, title = {Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102677}, pages = {67149 -- 67156}, year = {2015}, abstract = {In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.}, language = {en} } @article{MarmodeeKlerkdeKumkeetal.2008, author = {Marmod{\´e}e, Bettina and Klerk de, Joost and Kumke, Michael Uwe and Ariese, Freek and Gooijer, Cees}, title = {Spectroscopic investigations of complexes between Eu(III) and aromatic carboxylic ligands}, doi = {10.1016/j.jallcom.2007.04.150}, year = {2008}, abstract = {In order to obtain information on the number and symmetry of the different Eu3+ complexes formed with several hydroxybenzoic acids, ultra-low temperature luminescence measurements at 4.7 K were carried out. Hydroxybenzoic acids were used as simple model compounds for metal binding structures in humic substances (HS). Information on the complexes was extracted from high-resolution total luminescence spectra (TLS), which were obtained by scanning through the D-5(0) <-- F-7(0) transition of Eu(III) with a pulsed dye laser and measuring the emission in the wavelength range of the D- 5(0) --> F-7(0) and D-5(0) --> F-7(0) transitions simultaneously. By extracting the crystal field strength parameter N- v(B-2q) from the TLS, it was found that N-v(B-2q) was not directly correlated with the excitation energy. Further, the symmetry of the individual complexes formed was extracted from the experimental data. (C) 2007 Elsevier B.V. All rights reserved.}, language = {en} } @article{SchulerLipmanSteinbachetal.2005, author = {Schuler, Benjamin and Lipman, Everett A. and Steinbach, P. J. and Kumke, Michael Uwe and Eaton, W. A.}, title = {Polyproline and the "spectroscopic ruler" revisited with single-molecule fluorescence}, issn = {0027-8424}, year = {2005}, abstract = {To determine whether Forster 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 Forster theory, with polyproline treated as a rigid rod. At donor-acceptor distances much less than the Forster radius R-o, the observed efficiencies are lower than predicted, whereas at distances comparable to and greater than R-0, 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 Forster 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} } @article{TiseanuGessnerKumkeetal.2008, author = {Tiseanu, Carmen and Geßner, Andre and Kumke, Michael Uwe and Parvulescu, V.}, title = {Dehydration and rehydration effects on the photoluminescence properties of terbium-exchanged MFI type materials}, doi = {10.1016/j.jnoncrysol.2007.11.017}, year = {2008}, language = {en} } @article{TiseanuGessnerKumkeetal.2008, author = {Tiseanu, Carmen and Geßner, Andre and Kumke, Michael Uwe and Gagea, Bogdan and Parvulescu, Vasile Ion and Martens, Johan}, title = {Photoluminescence spectra and dynamics of lanthanide-doped microporous materials}, doi = {10.1016/j.jlumin.2007.10.018}, year = {2008}, abstract = {A series of terbium- and europium-exchanged microporous-mesoporous zeolite Socony Mobil Five (MFI)-type materials such as Zeotile-1 and Zeogrid with varying Si/Al ratios was investigated using FTIR, PXRD, adsorption- desorption isotherms of N-2 at 77 K and time-resolved luminescence spectroscopy. Silylation of the lanthanides-exchanged Zeotile-1 and Zeogrid with hexadecyl trimethoxysilanes via post-synthesis grafting was also studied. The results showed that the lanthanide's photoluminescence spectra and decays were modified due to silylation. The different silylation effects in Zeotile-1 and Zeogrid were correlated with the textural properties of the investigated materials. (C) 2007 Elsevier B.V. All rights reserved.}, language = {en} } @article{DoscheKumkeLoehmannsroebenetal.2004, author = {Dosche, Carsten and Kumke, Michael Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Ariese, Freek and Bader, Arjen N. and Gooijer, Cees and Miljanic, Ognjen S. and Iwamoto, M. and Vollhardt, K. Peter C. and Puchta, Ralph and Hommes, N. J. R. V.}, title = {Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]phenylene}, issn = {1463-9076}, year = {2004}, abstract = {Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [ 4] phenylene (D-3h [4]phenylene) were studied using laser-excited Shpol'skii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm(-1) and 1176 cm(-1), suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4] phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4] phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm(-1) probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state}, language = {en} } @article{TiseanuFrunzaKumke2004, author = {Tiseanu, Carmen and Frunza, L. and Kumke, Michael Uwe}, title = {Time-resolved photoluminescence analysis of distribution and migration of terbium ions in zeolites X}, year = {2004}, abstract = {The photoluminescence (PL) dynamics of terbium-exchanged zeolites X was investigated upon laser excitation at 355 nm. The results evidenced the presence of at least two terbium main environments with PL lifetimes varying between 391-411 and 753-770 mus. The two-site nature of terbium distribution in zeolites X permitted a quantitative analysis of the migration process of terbium ions inside the pores and cavities upon dehydration in air at 200 degreesC. Besides the increase of the PL lifetimes with about 30\% and 80\% compared to those of the hydrated zeolite, a fraction of almost 30\% of terbium ions was estimated to migrate from the supercages to the neighboring sodalites or hexagonal prisms. Our results evidenced for the first time the capability of time-resolved luminescence spectroscopy in quantitatively tracking for the intrazeolitic migration of lanthanides. (C) 2004 Elsevier B.V. All rights reserved}, language = {en} } @phdthesis{Kumke2005, author = {Kumke, Michael Uwe}, title = {Huminstoffe und organische Modellliganden und ihre Wechselwirkung mit Metallionen und polyzyklischen aromatischen Kohlenwasserstoffen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-6066}, school = {Universit{\"a}t Potsdam}, year = {2005}, abstract = {Immobilisierung bzw. Mobilisierung und Transport von Schadstoffen in der Umwelt, besonders in den Kompartimenten Boden und Wasser, sind von fundamentaler Bedeutung f{\"u}r unser ({\"U}ber)Leben auf der Erde. Einer der Hauptreaktionspartner f{\"u}r organische und anorganische Schadstoffe (Xenobiotika) in der Umwelt sind Huminstoffe (HS). HS sind Abbauprodukte pflanzlichen und tierischen Gewebes, die durch eine Kombination von chemischen und biologischen Ab- und Umbauprozessen entstehen. Bedingt durch ihre Genese stellen HS außerordentlich heterogene Stoffsysteme dar, die eine Palette von verschiedenartigen Wechselwirkungen mit Schadstoffen zeigen. Die Untersuchung der fundamentalen Wechselwirkungsmechanismen stellt ebenso wie deren quantitative Beschreibung h{\"o}chste Anforderungen an die Untersuchungsmethoden. Zur qualitativen und quantitativen Charakterisierung der Wechselwirkungen zwischen HS und Xenobiotika werden demnach analytische Methoden ben{\"o}tigt, die bei der Untersuchung von extrem heterogenen Systemen aussagekr{\"a}ftige Daten zu liefern verm{\"o}gen. Besonders spektroskopische Verfahren, wie z.B. lumineszenz-basierte Verfahren, besitzen neben der hervorragenden Selektivit{\"a}t und Sensitivit{\"a}t, auch eine Multidimensionalit{\"a}t (bei der Lumineszenz sind es die Beobachtungsgr{\"o}ßen Intensit{\"a}t IF, Anregungswellenl{\"a}nge lex, Emissionswellenl{\"a}nge lem und Fluoreszenzabklingzeit tF), die es gestattet, auch heterogene Systeme wie HS direkt zu untersuchen. Zur Charakterisierung k{\"o}nnen sowohl die intrinsischen Fluoreszenzeigenschaften der HS als auch die von speziell eingef{\"u}hrten Lumineszenzsonden verwendet werden. In beiden F{\"a}llen werden die zu Grunde liegenden fundamentalen Konzepte der Wechselwirkungen von HS mit Xenobiotika untersucht und charakterisiert. F{\"u}r die intrinsische Fluoreszenz der HS konnte gezeigt werden, dass neben molekularen Strukturen besonders die Verkn{\"u}pfung der Fluorophore im Gesamt-HS-Molek{\"u}l von Bedeutung ist. Konformative Freiheit und die Nachbarschaft zu als Energieakzeptor fungierenden HS-eigenen Gruppen sind wichtige Komponenten f{\"u}r die Charakteristik der HS-Fluoreszenz. Die L{\"o}schung der intrinsischen Fluoreszenz durch Metallkomplexierung ist demnach auch das Resultat der ver{\"a}nderten konformativen Freiheit der HS durch die gebundenen Metallionen. Es zeigte sich, dass abh{\"a}ngig vom Metallion sowohl L{\"o}schung als auch Verst{\"a}rkung der intrinsischen HS-Fluoreszenz beobachtet werden kann. Als extrinsische Lumineszenzsonden mit wohl-charakterisierten photophysikalischen Eigenschaften wurden polyzyklische aromatische Kohlenwasserstoffe und Lanthanoid-Ionen eingesetzt. Durch Untersuchungen bei sehr niedrigen Temperaturen (10 K) konnte erstmals die Mikroumgebung von an HS gebundenen hydrophoben Xenobiotika untersucht werden. Im Vergleich mit Raumtemperaturexperimenten konnte gezeigt werden, dass hydrophobe Xenobiotika an HS-gebunden in einer Mikroumgebung, die in ihrer Polarit{\"a}t analog zu kurzkettigen Alkoholen ist, vorliegen. F{\"u}r den Fall der Metallkomplexierung wurden Energietransferprozesse zwischen HS und Lanthanoidionen bzw. zwischen verschiedenen, gebundenen Lanthanoidionen untersucht. Basierend auf diesen Messungen k{\"o}nnen Aussagen {\"u}ber die beteiligten elektronischen Zust{\"a}nde der HS einerseits und Entfernungen von Metallbindungsstellen in HS selbst angeben werden. Es ist dabei zu beachten, dass die Experimente in L{\"o}sung bei realen Konzentrationen durchgef{\"u}hrt wurden. Aus Messung der Energietransferraten k{\"o}nnen direkte Aussagen {\"u}ber Konformations{\"a}nderungen bzw. Aggregationsprozesse von HS abgeleitet werden.}, subject = {Fluoreszenz}, language = {de} } @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{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{DoscheKumkeArieseetal.2003, author = {Dosche, Carsten and Kumke, Michael Uwe and Ariese, F. and Bader, Arjen N. and Gooijer, C. and Dosa, P. I. and Han, S. and Miljanic, O. S. and Vollhardt, K. Peter C. and Puchta, R. and Eikema Hommes, N. J. R. van}, title = {Shpol'skii spectroscopy and vibrational analysis of [N]phenylenes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13075}, year = {2003}, abstract = {Vibrationally resolved fluorescence spectra of four angular [N]phenylenes were recorded with laser excited Shpol'skii spectroscopy (LESS) in an n-octane matrix at 10 K. In general, the same vibrational frequencies were observed in the fluorescence excitation and emission spectra, indicating that the geometries of ground and electronically excited state are very similar. Because of intensity borrowing from the S2 state, vibrations of two different symmetries were observed in the fluorescence excitation spectra of angular [3]phenylene and zig-zag[5]phenylene. This finding allowed the location of the S2 state for these compounds. DFT calculations(RB3LYP/6-31G*) of the ground state vibrational frequencies were made. The calculated vibrational modes were in reasonably good agreement with the experimental data. A new very low-frequency vibration of approximately 100 cm-1 was predicted and experimentally confirmed for all [N]phenylenes investigated. This vibration seems to be unique for [N]phenylenes and is attributed to an in-plane movement of the carbon backbone.}, language = {de} } @misc{FrimmelKumke1998, author = {Frimmel, Fritz Hartmann and Kumke, Michael Uwe}, title = {Optische Parameter zur Stoffcharakterisierung vom Trinkwasser bis zum Abwasser}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13088}, year = {1998}, abstract = {Die Anwendung von optischen Parametern zur Stoffcharakterisierung wird diskutiert. Dabei ist der Schwerpunkt der Diskussion auf absorptions- und fluoreszenzspektroskopische Methoden gesetzt. Beide Methoden k{\"o}nnen schnell und zuverl{\"a}ssig - auch im on-line Betrieb - eingesetzt werden. Der Beitrag soll einen {\"U}berblick {\"u}ber die grundlegenden M{\"o}glichkeiten der Anwendung beider Methoden geben.}, language = {de} } @misc{KumkeFrimmel2002, author = {Kumke, Michael Uwe and Frimmel, Fritz Hartmann}, title = {Stationary and time-resolved fluorescence for humic substances characterization}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-12353}, year = {2002}, abstract = {Steady-state and time-resolved fluorescence methods were applied to investigate the fluorescence properties of humic substances of different origins. Using standard 2D emission and total luminescence spectra, fluorescence maxima, the width of the fluorescence band and a relative fluorescence quantum efficiency were determined. Different trends for fulvic acids and humic acids were observed indicating differences in the heterogeneity of the sample fractions. The complexity of the fluorescence decay of humic substances is discussed and compared to simple model compounds. The effect of oxidation of humic substances on their fluorescence properties is discussed as well.}, 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} } @misc{DoscheKumkeLoehmannsroebenetal.2004, author = {Dosche, Carsten and Kumke, Michael Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Ariese, F. and Bader, Arjen N. and Gooijer, C. and Miljanic, O. S. and Iwamoto, M. and Vollhardt, K. Peter C. and Puchta, R. ; van Eikema Hommes, N. J. R.}, title = {Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]Phenylene}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-11881}, year = {2004}, abstract = {Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [4]phenylene (D3h[4]phenylene) were studied using laser-excited Shpolskii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm-1 and 1176 cm-1, suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4]phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4]phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm-1 probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state.}, language = {de} } @article{PilarYesteCarlosHernandezGarridoKumkeetal.2022, author = {Pilar Yeste, Maria and Carlos Hernandez-Garrido, Juan and Kumke, Michael Uwe and Alvarado, Sarah and Cauqui, Miguel Angel and Juan Calvino, Jose and Primus, Philipp-Alexander}, title = {Low-temperature growth of reactive pyrochlore nanostructures on Zirconia-supported ceria}, series = {ACS applied nano materials}, volume = {5}, journal = {ACS applied nano materials}, number = {5}, publisher = {American Chemical Society}, address = {Washington}, issn = {2574-0970}, doi = {10.1021/acsanm.2c00416}, pages = {6316 -- 6326}, year = {2022}, abstract = {The use of a catalyst support for the design of nanoscale heterogeneous catalysts based on cerium oxide offers vast possibilities for future catalyst development, particularly with regard to an increased focus on the use of renewable biogas and an emerging hydrogen economy. In this study, zirconia-supported ceria catalysts were synthesized, activated by using different thermochemical treatments, and characterized by way of temperature-programmed reduction (TPR), oxygen storage capacity, Xray diffraction, electron microscopy, and luminescence spectroscopy using Eu3+ as a spectroscopic probe. Through reduction-oxidation pretreatment routines, reactive pyrochlore structures were created at temperatures as low as 600 degrees C and identified through TPR and electron microscopy experiments. A structural relationship and alignment of the crystal planes is revealed in high-resolution scanning transmission electron microscopy experiments through the digital diffraction patterns. Low-temperature pretreatment induces the formation of reactive pyrochlore domains under retention of the surface area of the catalyst system, and no further morphological changes are detected. Furthermore, the formation of pyrochlore domains achieved through severe reduction and mild reoxidation (SRMO) treatments is reversible. Over multiple alternating SRMO and severe reduction and severe reoxidation (SRSO) treatments, europium spectroscopy and TPR results indicate that pyrochlore structures are recreated over consecutive treatments, whenever the mild oxidation step at 500 degrees C is the last treatment (SRMO, SRMO-SRSO-SRMO, etc.).}, language = {en} } @article{PrimusMenskiYesteetal.2015, author = {Primus, Philipp-Alexander and Menski, Antonia and Yeste, Maria Pilar and Cauqui, Miguel Angel and Kumke, Michael Uwe}, title = {Fluorescence Line-Narrowing Spectroscopy as a Tool to Monitor Phase Transitions and Phase Separation in Efficient Nanocrystalline CexZr1-xO2:Eu3+ Catalyst Materials}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b01271}, pages = {10682 -- 10692}, year = {2015}, abstract = {Despite the wide range of industrial applications for ceria-zirconia mixed oxides (CexZr1-xO2), the complex correlation between their atomic structure and catalytic performance is still under debate. Catalytically interesting CexZr1-xO2 nanomaterials can form homogeneous solid solutions and, depending on the composition, show phase separation under the formation of small domains. The characterization of homogeneity and atomic structure of these materials remains a major challenge. High-resolution emission spectroscopy recorded under cryogenic conditions using Eu3+ as a structural probe in doped CeZrO2 nanoparticles offers an effective way to identify the different atomic environments of the Eu3+ dopants and, subsequently, to monitor structural parameters of the ceria-zirconia mixed oxides. It is found that, in stoichiometric CeZrO2:Eu3+, phase separation occurs at elevated temperatures beginning with the gradual formation of (pseudo)cubic crystallites in the amorphous materials at 500 degrees C and a sudden phase separation into tetragonal, zirconia-rich and cubic, ceria-rich domains over 900 degrees C. The presented technique allows us to easily monitor subtle changes even in amorphous, high surface area samples, yielding structural information not accessible by conventional techniques such as X-ray diffraction (XRD) and Raman. Moreover, in reference experiments investigating the reducibility of largely unordered Ce0.2Zr0.8O2:Eu3+, the main reduction peak in temperature-programmed reduction measurements appeared at exceptionally low temperatures below 200 degrees C, thus suggesting the outstanding potential of this oxide to activate catalytic oxidation reactions. This effect was found to be dependent on the amount of Eu3+ dopant introduced into the CeZrO2 matrix as well as to be connected to the atomic structure of the catalyst material.}, language = {en} } @article{PrimusRitschelSigueenzaetal.2014, author = {Primus, Philipp-Alexander and Ritschel, Thomas and Sigueenza, Pilar Y. and Cauqui, Miguel Angel and Hernandez-Garrido, Juan Carlos and Kumke, Michael Uwe}, title = {High-resolution spectroscopy of europium-doped ceria as a tool to correlate structure and catalytic activity}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {118}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {40}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/jp505467r}, pages = {23349 -- 23360}, year = {2014}, abstract = {Site-selective emission spectra of Eu3+-doped CeO2 nanoparticles up to the D-5(0) - F-7(5) transition were recorded under cryogenic conditions to identify the local structure around the Eu3+ dopants in ceria. It is found that pretreatment conditions are crucial for the redistribution of dopants from a broad variety of environments to six well-defined lattice sites. The influence of the dopant and the host structure on the catalytic activity was investigated. A relationship between structure and reactivity is discussed. It is shown that oxygen transport is most efficient in particles with a pronounced amorphous character.}, language = {en} } @misc{LopezdeGuerenuBastianWessigetal.2019, author = {L{\´o}pez de Guere{\~n}u, Anna and Bastian, Philipp and Wessig, Pablo and John, Leonard and Kumke, Michael Uwe}, title = {Energy transfer between tm-doped upconverting nanoparticles and a small organic dye with large stokes shift}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch Naturwissenschaftliche Reihe}, number = {961}, issn = {1866-8372}, doi = {10.25932/publishup-47224}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-472240}, pages = {19}, year = {2019}, abstract = {Lanthanide-doped upconverting nanoparticles (UCNP) are being extensively studied for bioapplications due to their unique photoluminescence properties and low toxicity. Interest in RET applications involving UCNP is also increasing, but due to factors such as large sizes, ion emission distributions within the particles, and complicated energy transfer processes within the UCNP, there are still many questions to be answered. In this study, four types of core and core-shell NaYF4-based UCNP co-doped with Yb3+ and Tm3+ as sensitizer and activator, respectively, were investigated as donors for the Methyl 5-(8-decanoylbenzo[1,2-d:4,5-d ']bis([1,3]dioxole)-4-yl)-5-oxopentanoate (DBD-6) dye. The possibility of resonance energy transfer (RET) between UCNP and the DBD-6 attached to their surface was demonstrated based on the comparison of luminescence intensities, band ratios, and decay kinetics. The architecture of UCNP influenced both the luminescence properties and the energy transfer to the dye: UCNP with an inert shell were the brightest, but their RET efficiency was the lowest (17\%). Nanoparticles with Tm3+ only in the shell have revealed the highest RET efficiencies (up to 51\%) despite the compromised luminescence due to surface quenching.}, language = {en} } @article{HaubitzJohnFreyseetal.2020, author = {Haubitz, Toni and John, Leonard and Freyse, Daniel and Wessig, Pablo and Kumke, Michael Uwe}, title = {Investigating the Sulfur "Twist" on the Photophysics of DBD Dyes}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {124}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, number = {22}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.0c01880}, pages = {4345 -- 4353}, year = {2020}, abstract = {The so-called DBD ([1,3]dioxolo[4,5-f][1,3]benzodioxole) dyes are a new class of fluorescent dyes, with tunable photophysical properties like absorption, fluorescence lifetime, and Stokes shift. With the development of sulfur based DBDs, this dye class is extended even further for possible applications in spectroscopy and microscopy. In this paper we are investigating the basic photophysical properties and their implications for future applications for S-4-DBD as well as O-4-DBD. On the basis of time-resolved laser fluorescence spectroscopy, transient absorption spectroscopy, and UV/vis-spectroscopy, we determined the rate constants of the radiative and nonradiative deactivation processes as well as the energy of respective electronic states involved in the electronic deactivation of S-4-DBD and of O-4-DBD. For S-4-DBD we unraveled the triplet formation with intersystem crossing quantum yields of up to 80\%. By TD-DFT calculations we estimated a triplet energy of around 13500-14700 cm(-1) depending on the DBD dye and solvent. Through solvent dependent measurements, we found quadrupole moments in the range of 2 B.}, language = {en} }