TY - JOUR A1 - Kuke, S. A1 - Marmodee, Bettina A1 - Eidner, Sascha A1 - Schilde, Uwe A1 - Kumke, Michael Uwe T1 - Intramolecular deactivation processes in complexes of salicylic acid or glycolic acid with Eu(III) N2 - The complexation of Eu(III) by 2-hydroxy benzoic acid (2HB) or glycolic acid (GL) was investigated using steady- state and time-resolved laser spectroscopy. Experiments were carried out in H2O as well as in D2O in the temperature range of View the MathML source. The Eu(III) luminescence spectra and luminescence decay times were evaluated with respect to the temperature dependence of (i) the luminescence decay time ;, (ii) the energy of the View the MathML source transition, (iii) the width of the View the MathML source transition, and (iv) the asymmetry ratio calculated from the luminescence intensities of the View the MathML source and View the MathML source transition, respectively. The differences in ligand-related luminescence quenching are discussed. Based on the temperature dependence of the luminescence decay times an activation energy for the ligand-specific non-radiative deactivation in Eu(III)-2HB or Eu(III)-GL complexes was determined. It is stressed that ligand-specific quenching processes (other than OH quenching induced by water molecules) need to be determined and considered in detail, in order to extract speciation- relevant information from luminescence data (e.g., estimation of the number of water molecules nH2O in the first coordination sphere of Eu(III)). In case of 2HB, conclusions drawn from the evaluation of the Eu(III) luminescence are compared with results of a X-ray structure analysis. Y1 - 2010 UR - http://www.sciencedirect.com/science/article/pii/S1386142510000144 SN - 0584-8539 ER - TY - JOUR A1 - Alrefai, Anas A1 - Mondal, Suvendu Sekhar A1 - Wruck, Alexander A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Brandt, Philipp A1 - Janiak, Christoph A1 - Schoenfeld, Sophie A1 - Weber, Birgit A1 - Rybakowski, Lawrence A1 - Herrman, Carmen A1 - Brennenstuhl, Katlen A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Behrens, Karsten A1 - Günter, Christina A1 - Müller, Holger A1 - Holdt, Hans-Jürgen T1 - Hydrogen-bonded supramolecular metal-imidazolate frameworks: gas sorption, magnetic and UV/Vis spectroscopic properties JF - Journal of Inclusion Phenomena and Macrocyclic Chemistry N2 - By varying reaction parameters for the syntheses of the hydrogen-bonded metal-imidazolate frameworks (HIF) HIF-1 and HIF-2 (featuring 14 Zn and 14 Co atoms, respectively) to increase their yields and crystallinity, we found that HIF-1 is generated in two different frameworks, named as HIF-1a and HIF-1b. HIF-1b is isostructural to HIF-2. We determined the gas sorption and magnetic properties of HIF-2. In comparison to HIF-1a (Brunauer-Emmett-Teller (BET) surface area of 471m(2) g(-1)), HIF-2 possesses overall very low gas sorption uptake capacities [BET(CO2) surface area=85m(2) g(-1)]. Variable temperature magnetic susceptibility measurement of HIF-2 showed antiferromagnetic exchange interactions between the cobalt(II) high-spin centres at lower temperature. Theoretical analysis by density functional theory confirmed this finding. The UV/Vis-reflection spectra of HIF-1 (mixture of HIF-1a and b), HIF-2 and HIF-3 (with 14 Cd atoms) were measured and showed a characteristic absorption band centered at 340nm, which was indicative for differences in the imidazolate framework. KW - Gas-sorption KW - Ligand design KW - Magnetic properties KW - Supramolecular chemistry KW - Solvothermal synthesis Y1 - 2019 U6 - https://doi.org/10.1007/s10847-019-00926-6 SN - 1388-3127 SN - 1573-1111 VL - 94 IS - 3-4 SP - 155 EP - 165 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Eisold, Ursula A1 - Kupstat, Annette A1 - Klier, Dennis Tobias A1 - Primus, Philipp-A. A1 - Pschenitza, Michael A1 - Niessner, Reinhard A1 - Knopp, Dietmar A1 - Kumke, Michael Uwe T1 - Probing the physicochemical interactions of 3-hydroxy-benzo[a]pyrene with different monoclonal and recombinant antibodies by use of fluorescence line-narrowing spectroscopy JF - Analytical & bioanalytical chemistry N2 - Characterization of interactions between antigens and antibodies is of utmost importance both for fundamental understanding of the binding and for development of advanced clinical diagnostics. Here, fluorescence line-narrowing (FLN) spectroscopy was used to study physicochemical interactions between 3-hydroxybenzo[a]pyrene (3OH-BaP, as antigen) and a variety of solvent matrices (as model systems) or anti-polycyclic aromatic hydrocarbon antibodies (anti-PAH). We focused the studies on the specific physicochemical interactions between 3OH-BaP and different, previously obtained, monoclonal and recombinant anti-PAH antibodies. Control experiments performed with non-binding monoclonal antibodies and bovine serum albumin (BSA) indicated that nonspecific interactions did not affect the FLN spectrum of 3OH-BaP. The spectral positions and relative intensities of the bands in the FLN spectra are highly dependent on the molecular environment of the 3OH-BaP. The FLN bands correlate with different vibrational modes of 3OH-BaP which are affected by interactions with the molecular environment (pi-pi interactions, H-bonding, or van-der-Waals forces). Although the analyte (3OH-BaP) was the same for all the antibodies investigated, different binding interactions could be identified from the FLN spectra on the basis of structural flexibility and conformational multiplicity of the antibodies' paratopes. KW - FLNS KW - Antibody KW - Paratope KW - Hapten KW - Polycyclic aromatic hydrocarbons Y1 - 2014 U6 - https://doi.org/10.1007/s00216-013-7584-8 SN - 1618-2642 SN - 1618-2650 VL - 406 IS - 14 SP - 3387 EP - 3394 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Kumke, Michael Uwe A1 - Eidner, Sascha A1 - Krüger, Tobias T1 - Fluorescence quenching and luminescence sensitization in complexes of Tb3+ and Eu3+ with humic substances N2 - Intrinsic fluorescence quenching of humic substances (HS) and the sensitization of Ln(3+) luminescence (Ln3+ Tb3+, Eu3+) in HS complexes were investigated. Both measurements yielded complementary information on the complexation of metals by HS. Large differences between fulvic acids(FA)and humic acids (HA) were found. From time-resolved luminescence measurements it is concluded that a combination of energy transfer and energy back transfer between HS and Ln(3+) is responsible for the observed luminescence decay characteristics. In the case of Eu3+, an additional participation of charge-transfer states is suggested. A new concept for the evaluation of the sensitized luminescence decays of Ln(3+) was adapted Y1 - 2005 ER - TY - JOUR A1 - Roth, Martin M. A1 - Löhmannsröben, Hans-Gerd A1 - Kelz, A. A1 - Kumke, Michael Uwe T1 - innoFSPEC : fiber optical spectroscopy and sensing Y1 - 2008 SN - 978-0-819-47228-1 ER - TY - JOUR A1 - Hesse, Julia A1 - Klier, Dennis Tobias A1 - Sgarzi, Massimo A1 - Nsubuga, Anne A1 - Bauer, Christoph A1 - Grenzer, Joerg A1 - Hübner, Rene A1 - Wislicenus, Marcus A1 - Joshi, Tanmaya A1 - Kumke, Michael Uwe A1 - Stephan, Holger T1 - Rapid Synthesis of Sub-10nm Hexagonal NaYF4-Based Upconverting Nanoparticles using Therminol((R))66 JF - ChemistryOpen : including thesis treasury N2 - We report a simple one-pot method for the rapid preparation of sub-10nm pure hexagonal (-phase) NaYF4-based upconverting nanoparticles (UCNPs). Using Therminol((R))66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd3+ and Yb3+ sensitizer ions and Er3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects. KW - core-shell materials KW - lanthanides KW - nanostructures KW - photoluminescence KW - upconversion Y1 - 2018 U6 - https://doi.org/10.1002/open.201700186 SN - 2191-1363 VL - 7 IS - 2 SP - 159 EP - 168 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Burek, Katja A1 - Eidner, Sascha A1 - Kuke, Stefanie A1 - Kumke, Michael Uwe T1 - Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight JF - Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy N2 - The luminescence of Lanthanide(Ill) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and.Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(Ill) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K <= T <= 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M <= 1 <= 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites. KW - Humic substance KW - Model ligand KW - Metal complexation KW - Benzoic acids KW - Intramolecular deactivation Y1 - 2018 U6 - https://doi.org/10.1016/j.saa.2017.09.012 SN - 1386-1425 VL - 191 SP - 36 EP - 49 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Haubitz, Toni A1 - Fudickar, Werner A1 - Linker, Torsten A1 - Kumke, Michael Uwe T1 - pH-sensitive fluorescence switching of pyridylanthracenes BT - the effect of the isomeric pattern JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - 9,10-substituted anthracenes are known for their useful optical properties like fluorescence, which makes them frequently used probes in sensing applications. In this article, we investigate the fundamental photophysical properties of three pyridyl-substituted variants. The nitrogen atoms in the pyridinium six-membered rings are located in the ortho-, meta-, and para-positions in relation to the anthracene core. Absorption, fluorescence, and transient absorption measurements were carried out and were complemented by theoretical calculations. We monitored the photophysics of the anthracene derivatives in chloroform and water investigating the protonated as well as their nonprotonated forms. We found that the optical properties of the nonprotonated forms are strongly determined by the anthracene chromophore, with only small differences to other 9,10-substituted anthracenes, for example diphenyl anthracene. In contrast, protonation leads to a strong decrease in fluorescence intensity and lifetime. Transient absorption measurements and theoretical calculations revealed the formation of a charge-transfer state in the protonated chromophores, where electron density is shifted from the anthracene moiety toward the protonated pyridyl substituents. While the para- and ortho-derivatives' charge transfer is still moderately fluorescent, the meta-derivative is affected much stronger and shows nearly no fluorescence. This nitrogen-atom-position-dependent sensitivity to hydronium activity makes a combination of these fluorophores very attractive for pH-sensing applications covering a broadened pH range. KW - Absorption KW - Aromatic compounds KW - Fluorescence KW - Hydrocarbons KW - Reaction mechanisms Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpca.0c09911 SN - 1089-5639 SN - 1520-5215 VL - 124 IS - 52 SP - 11017 EP - 11024 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Schott, Juliane A1 - Kretzschmar, Jerome A1 - Acker, Margret A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Drobot, Björn A1 - Barkleit, Astrid A1 - Taut, Steffen A1 - Brendler, Vinzenz A1 - Stumpf, Thorsten T1 - Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution N2 - In the presence of polyborates (detected by 11B-NMR) the formation of a weak Eu(III) borate complex (lg β11 ∼ 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 277 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-98774 ER - TY - JOUR A1 - Steinbrück, Dörte A1 - Rasch, Claudia A1 - Kumke, Michael Uwe T1 - Photophysics of Ochratoxin A in aqueous solution Y1 - 2008 ER - TY - GEN A1 - Kumke, Michael Uwe A1 - Klier, Dennis Tobias T1 - Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 304 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-102677 SP - 67149 EP - 67156 ER - TY - JOUR A1 - Marmodée, Bettina A1 - Klerk de, Joost A1 - Kumke, Michael Uwe A1 - Ariese, Freek A1 - Gooijer, Cees T1 - Spectroscopic investigations of complexes between Eu(III) and aromatic carboxylic ligands N2 - 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. Y1 - 2008 U6 - https://doi.org/10.1016/j.jallcom.2007.04.150 ER - TY - JOUR A1 - Schuler, Benjamin A1 - Lipman, Everett A. A1 - Steinbach, P. J. A1 - Kumke, Michael Uwe A1 - Eaton, W. A. T1 - Polyproline and the "spectroscopic ruler" revisited with single-molecule fluorescence N2 - 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 Y1 - 2005 SN - 0027-8424 ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Geßner, Andre A1 - Kumke, Michael Uwe A1 - Parvulescu, V. T1 - Dehydration and rehydration effects on the photoluminescence properties of terbium-exchanged MFI type materials Y1 - 2008 U6 - https://doi.org/10.1016/j.jnoncrysol.2007.11.017 ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Geßner, Andre A1 - Kumke, Michael Uwe A1 - Gagea, Bogdan A1 - Parvulescu, Vasile Ion A1 - Martens, Johan T1 - Photoluminescence spectra and dynamics of lanthanide-doped microporous materials N2 - 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. Y1 - 2008 UR - http://www.sciencedirect.com/science/article/pii/S0022231307003262 U6 - https://doi.org/10.1016/j.jlumin.2007.10.018 ER - TY - JOUR A1 - Dosche, Carsten A1 - Kumke, Michael Uwe A1 - Löhmannsröben, Hans-Gerd A1 - Ariese, Freek A1 - Bader, Arjen N. A1 - Gooijer, Cees A1 - Miljanic, Ognjen S. A1 - Iwamoto, M. A1 - Vollhardt, K. Peter C. A1 - Puchta, Ralph A1 - Hommes, N. J. R. V. T1 - Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]phenylene N2 - 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 Y1 - 2004 SN - 1463-9076 ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Frunza, L. A1 - Kumke, Michael Uwe T1 - Time-resolved photoluminescence analysis of distribution and migration of terbium ions in zeolites X N2 - 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 Y1 - 2004 ER - TY - THES A1 - Kumke, Michael Uwe T1 - Huminstoffe und organische Modellliganden und ihre Wechselwirkung mit Metallionen und polyzyklischen aromatischen Kohlenwasserstoffen T1 - Humic substances and organic model ligands – Interactions with metal ions and polycyclic aromatic hydrocarbons N2 - Immobilisierung bzw. Mobilisierung und Transport von Schadstoffen in der Umwelt, besonders in den Kompartimenten Boden und Wasser, sind von fundamentaler Bedeutung für unser (Über)Leben auf der Erde. Einer der Hauptreaktionspartner für 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 höchste Anforderungen an die Untersuchungsmethoden. Zur qualitativen und quantitativen Charakterisierung der Wechselwirkungen zwischen HS und Xenobiotika werden demnach analytische Methoden benötigt, die bei der Untersuchung von extrem heterogenen Systemen aussagekräftige Daten zu liefern vermögen. Besonders spektroskopische Verfahren, wie z.B. lumineszenz-basierte Verfahren, besitzen neben der hervorragenden Selektivität und Sensitivität, auch eine Multidimensionalität (bei der Lumineszenz sind es die Beobachtungsgrößen Intensität IF, Anregungswellenlänge lex, Emissionswellenlänge lem und Fluoreszenzabklingzeit tF), die es gestattet, auch heterogene Systeme wie HS direkt zu untersuchen. Zur Charakterisierung können sowohl die intrinsischen Fluoreszenzeigenschaften der HS als auch die von speziell eingeführten Lumineszenzsonden verwendet werden. In beiden Fällen werden die zu Grunde liegenden fundamentalen Konzepte der Wechselwirkungen von HS mit Xenobiotika untersucht und charakterisiert. Für die intrinsische Fluoreszenz der HS konnte gezeigt werden, dass neben molekularen Strukturen besonders die Verknüpfung der Fluorophore im Gesamt-HS-Molekül von Bedeutung ist. Konformative Freiheit und die Nachbarschaft zu als Energieakzeptor fungierenden HS-eigenen Gruppen sind wichtige Komponenten für die Charakteristik der HS-Fluoreszenz. Die Löschung der intrinsischen Fluoreszenz durch Metallkomplexierung ist demnach auch das Resultat der veränderten konformativen Freiheit der HS durch die gebundenen Metallionen. Es zeigte sich, dass abhängig vom Metallion sowohl Löschung als auch Verstärkung 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 Polarität analog zu kurzkettigen Alkoholen ist, vorliegen. Für den Fall der Metallkomplexierung wurden Energietransferprozesse zwischen HS und Lanthanoidionen bzw. zwischen verschiedenen, gebundenen Lanthanoidionen untersucht. Basierend auf diesen Messungen können Aussagen über die beteiligten elektronischen Zustände der HS einerseits und Entfernungen von Metallbindungsstellen in HS selbst angeben werden. Es ist dabei zu beachten, dass die Experimente in Lösung bei realen Konzentrationen durchgeführt wurden. Aus Messung der Energietransferraten können direkte Aussagen über Konformationsänderungen bzw. Aggregationsprozesse von HS abgeleitet werden. N2 - Transport and fate of xenobiotics in the environment, especially in water and soil, are of utmost importance for life on earth. A major reaction partner for xenobiotics in the environment are humic substances (HS). HS are degradation products of plant and animal tissue, which are formed in a combination of subsequent chemical and/or biochemical processes. Because of the complex history of their origin HS are extremely heterogeneous mixtures of different compounds. Consequently, they posses a great variety of interaction capabilities with various xenobiotics. The investigations of the fundamental interaction mechanisms between HS and xenobiotics make high demands on the analytical techniques used. Especially spectroscopic techniques are promising for the investigation of interaction mechanisms in complex systems. Luminescence spectroscopy has the great advantage of outstanding sensitivity and of multidimensionality, which in principle allows the investigation of HS under environmental relevant conditions. For the characterisation of interaction processes of HS with xenobiotics the intrinsic fluorescence of HS as well as the luminescence of extrinsic probes can be used. The intrinsic HS fluorescence is determined by the molecular structure as well as the connection of the basic fluorophores. Conformational freedom as well as the presence of energy accepting groups in the neighbourhood of the fluorophores are highly important for the overall intrinsic HS fluorescence. The presence of metal ions can either quench or enhance the intrinsic HS fluorescence, which depends on the metal ion as well as on the origin of the HS investigated. While in most cases Al3+ ions enhance the intrinsic HS fluorescence, Ln3+ ions induce a fluorescence quenching. Polycyclic aromatic hydrocarbons were used as extrinsic fluorescence probes in order to characterize the interaction of HS and hydrophobic organic xenobiotics. In investigations at ultra-low temperatures (10 K) it could be shown that pyrene is bound in a HS microenvironment with an polarity which resembles that of small alcohols (e.g., butanol). In case of metal complexation, the lanthanide ions Eu3+ and Tb3+ were used as luminescence probes. Due to the outstanding luminescence properties of those ions, information about metal binding sites in HS were obtained. Based on the measurements of intramolecular and intermolecular energy transfer processes average distances of metal binding sites were deduced. KW - Fluoreszenz KW - Huminstoffe KW - Lanthanoide KW - Huminstoffe KW - Fluoreszenz KW - Lanthanoide KW - Resonanzenergietransfer KW - Lumineszenzsonden KW - Fluorescence KW - humic substances KW - resonance energy transfer KW - luminescence probes KW - lanthanides Y1 - 2005 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-6066 ER - TY - GEN A1 - Schuler, Benjamin A1 - Lipman, Everett A. A1 - Steinbach, Peter J. A1 - Kumke, Michael Uwe A1 - Eaton, William A. T1 - Polyproline and the "spectroscopic ruler" revisited with single-molecule fluorescence N2 - To determine whether Förster 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 Förster theory, with polyproline treated as a rigid rod. At donor–acceptor distances much less than the Förster 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 Förster 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 008 KW - Förster resonance energy transfer KW - molecular dynamics KW - polypeptide KW - FRET Y1 - 2005 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12229 ER - TY - GEN A1 - Engelhard, Sonja A1 - Kumke, Michael Uwe A1 - Löhmannsröben, Hans-Gerd T1 - OPQS – optical process and quality sensing : exemplary applications in the beerbrewing and polyurethane foaming processes N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 004 KW - process analytical technology KW - beer KW - biomass KW - foam analysis KW - NIR spectroscopy KW - fluorescence quenching KW - photon density wave spectroscopy Y1 - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12191 ER - TY - GEN A1 - Dosche, Carsten A1 - Kumke, Michael Uwe A1 - Ariese, F. A1 - Bader, Arjen N. A1 - Gooijer, C. A1 - Dosa, P. I. A1 - Han, S. A1 - Miljanic, O. S. A1 - Vollhardt, K. Peter C. A1 - Puchta, R. A1 - Eikema Hommes, N. J. R. van T1 - Shpol’skii spectroscopy and vibrational analysis of [N]phenylenes N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 024 Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-13075 ER - TY - GEN A1 - Frimmel, Fritz Hartmann A1 - Kumke, Michael Uwe T1 - Optische Parameter zur Stoffcharakterisierung vom Trinkwasser bis zum Abwasser N2 - Die Anwendung von optischen Parametern zur Stoffcharakterisierung wird diskutiert. Dabei ist der Schwerpunkt der Diskussion auf absorptions- und fluoreszenzspektroskopische Methoden gesetzt. Beide Methoden können schnell und zuverlässig – auch im on-line Betrieb – eingesetzt werden. Der Beitrag soll einen Überblick über die grundlegenden Möglichkeiten der Anwendung beider Methoden geben. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 025 KW - Absorptionsspektroskopie KW - SAK KW - Fluoreszenzspektroskopie KW - Summenparameter KW - Huminstoffe KW - polyzyklische aromatische Kohlenwasserstoffe Y1 - 1998 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-13088 ER - TY - GEN A1 - Kumke, Michael Uwe A1 - Frimmel, Fritz Hartmann T1 - Stationary and time-resolved fluorescence for humic substances characterization N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 014 Y1 - 2002 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12353 ER - TY - GEN A1 - Billard, Isabelle A1 - Ansoborlo, Eric A1 - Apperson, Kathleen A1 - Arpigny, Sylvie A1 - Azenha, M. Emilia A1 - Birch, David A1 - Bros, Pascal A1 - Burrows, Hugh D. A1 - Choppin, Gregory A1 - Kumke, Michael Uwe T1 - Aqueous solutions of Uranium(VI) as studied by time-resolved emission spectroscopy : a Round-Robin Test N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 005 KW - uranium (VI) KW - intercomparison KW - speciation Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12318 ER - TY - GEN A1 - Dosche, Carsten A1 - Kumke, Michael Uwe A1 - Löhmannsröben, Hans-Gerd A1 - Ariese, F. A1 - Bader, Arjen N. A1 - Gooijer, C. A1 - Miljanic, O. S. A1 - Iwamoto, M. A1 - Vollhardt, K. Peter C. A1 - Puchta, R. ; van Eikema Hommes, N. J. R. T1 - Deuteration effects on the vibronic structure of the fluorescence spectra and the internal conversion rates of triangular [4]Phenylene N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 002 Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-11881 ER - TY - JOUR A1 - Pilar Yeste, Maria A1 - Carlos Hernandez-Garrido, Juan A1 - Kumke, Michael Uwe A1 - Alvarado, Sarah A1 - Cauqui, Miguel Angel A1 - Juan Calvino, Jose A1 - Primus, Philipp-Alexander T1 - Low-temperature growth of reactive pyrochlore nanostructures on Zirconia-supported ceria BT - implications for improved catalytic behavior JF - ACS applied nano materials N2 - 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.). KW - pyrochlore KW - nanocomposite KW - ceria KW - zirconia KW - supported catalyst KW - oxygen KW - storage capacity Y1 - 2022 U6 - https://doi.org/10.1021/acsanm.2c00416 SN - 2574-0970 VL - 5 IS - 5 SP - 6316 EP - 6326 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Primus, Philipp-Alexander A1 - Menski, Antonia A1 - Yeste, Maria Pilar A1 - Cauqui, Miguel Angel A1 - Kumke, Michael Uwe T1 - Fluorescence Line-Narrowing Spectroscopy as a Tool to Monitor Phase Transitions and Phase Separation in Efficient Nanocrystalline CexZr1-xO2:Eu3+ Catalyst Materials JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - 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. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jpcc.5b01271 SN - 1932-7447 VL - 119 IS - 19 SP - 10682 EP - 10692 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Primus, Philipp-Alexander A1 - Ritschel, Thomas A1 - Sigueenza, Pilar Y. A1 - Cauqui, Miguel Angel A1 - Hernandez-Garrido, Juan Carlos A1 - Kumke, Michael Uwe T1 - High-resolution spectroscopy of europium-doped ceria as a tool to correlate structure and catalytic activity JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - 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. Y1 - 2014 U6 - https://doi.org/10.1021/jp505467r SN - 1932-7447 VL - 118 IS - 40 SP - 23349 EP - 23360 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - López de Guereñu, Anna A1 - Bastian, Philipp A1 - Wessig, Pablo A1 - John, Leonard A1 - Kumke, Michael Uwe T1 - Energy transfer between tm-doped upconverting nanoparticles and a small organic dye with large stokes shift T2 - Postprints der Universität Potsdam : Mathematisch Naturwissenschaftliche Reihe N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 961 KW - resonance energy transfer KW - DBD dye KW - core shell UCNP KW - time-resolved luminescence Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-472240 SN - 1866-8372 IS - 961 ER - TY - JOUR A1 - Haubitz, Toni A1 - John, Leonard A1 - Freyse, Daniel A1 - Wessig, Pablo A1 - Kumke, Michael Uwe T1 - Investigating the Sulfur "Twist" on the Photophysics of DBD Dyes JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - 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. Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpca.0c01880 SN - 1089-5639 SN - 1520-5215 VL - 124 IS - 22 SP - 4345 EP - 4353 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lippold, Holger A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Lippmann-Pipke, Johanna T1 - Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of Tb-160 as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable Tb-159 or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of Tb-160 was introduced prior to saturation with Tb-159, the expected partial desorption of Tb-160 occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive transport models. KW - Humic substances KW - Metal complexation KW - Kinetics KW - Reversibility KW - Isotope exchange KW - Dynamic equilibrium Y1 - 2016 U6 - https://doi.org/10.1016/j.gca.2016.10.019 SN - 0016-7037 SN - 1872-9533 VL - 197 SP - 62 EP - 70 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Haubitz, Toni A1 - Tsushima, Satoru A1 - Steudtner, Robin A1 - Drobot, Björn A1 - Geipel, Gerhard A1 - Stumpf, Thorsten A1 - Kumke, Michael Uwe T1 - Ultrafast Transient Absorption Spectroscopy of UO(2)(2+)and [UO2Cl](+) JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - For the only water coordinated "free" uranyl (VI) aquo ion in perchlorate solution we identified and assigned several different excited states and showed that the (3)Delta state is the luminescent triplet state from transient absorption spectroscopy. With additional data from other spectroscopic methods (TRLFS, UV/vis) we generated a detailed Jablonski diagram and determined rate constants for several state transitions, like the inner conversion rate constant from the (3)Phi state to the (3)Delta state transition to be 0.35 ps(-1). In contrast to luminescence measurements, it was possible to observe the highly quenched uranyl(VI) ion in highly concentrated chloride solution by TAS and we were able to propose a dynamic quenching mechanism, where chloride complexation is followed by the charge transfer from the excited state uranyl(VI) to chloride. This proposed quenching route is supported by TD-DFT calculations. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpca.8b05567 SN - 1089-5639 VL - 122 IS - 35 SP - 6970 EP - 6977 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hoang, Hoa T. A1 - Haubitz, Toni A1 - Kumke, Michael Uwe T1 - Photophysics of "Floppy" Dyadsas Potential Biomembrane Probes JF - Journal of fluorescence N2 - In the study a dyad (C6 probe), constructed of two dyes with highly different hydrophobicities, was investigated by steady-state and time-resolved spectroscopic techniques in chloroform, methanol, and in phospholipid vesicles, respectively. The dyad was built on two dyes: the lipophilic benzo[a]pyrene (BaP) and the hydrophilic sulforhodamine B (SRB). The dyes were linked via a short, but flexible alkyl chain (six C-atoms). Based on their spectroscopic properties, BaP and SRB showed a very efficient non-radiative resonance energy transfer in solution. Incorporation into a lipid bilayer limited the relative flexibility (degree of freedom) between donor and acceptor and was used for the investigation of fundamental photophysical aspects (especially of FRET) as well as to elucidate the potential of the dyad to probe the interface of vesicles (or cells). The location of the two dyes in vesicles and their respective accessibility for interactions with dye-specific antibodies was investigated. Based on the alteration of the anisotropy, on the rotational correlation time as well as on the diffusion coefficient the incorporation of the C6 probe into the vesicles was evaluated. Especially the limitation in the relative movements of the two dyes was considered and used to differentiate between potential parameters, that influence the energy transfer in the dyad. Transient absorption spectroscopy (TAS) and pulsed-interleave single molecule fluorescence experiments were performed to better understand the intramolecular interactions in the dyad. Finally, in a showcase for a biosensing application of the dyads, the binding of an SRB-specific antibody was investigated when the dyad was incorporated in vesicles. KW - Forster resonance energy transfer(FRET) KW - Antibody binding KW - Vesicles KW - Anisotropy KW - Fluorescence correlation KW - Single molecule fluorescence KW - Transient absorption KW - Pulsed interleaved excitation Y1 - 2018 U6 - https://doi.org/10.1007/s10895-018-2286-4 SN - 1053-0509 SN - 1573-4994 VL - 28 IS - 5 SP - 1225 EP - 1237 PB - Springer CY - New York ER - TY - JOUR A1 - Müller, Katharina A1 - Foerstendorf, Harald A1 - Steudtner, Robin A1 - Tsushima, Satoru A1 - Kumke, Michael Uwe A1 - Lefèvre, Grégory A1 - Rothe, Jörg A1 - Mason, Harris A1 - Szabó, Zoltán A1 - Yang, Ping A1 - Adam, Christian K. R. A1 - André, Rémi A1 - Brennenstuhl, Katlen A1 - Chiorescu, Ion A1 - Cho, Herman M. A1 - Creff, Gaëlle A1 - Coppin, Frédéric A1 - Dardenne, Kathy A1 - Den Auwer, Christophe A1 - Drobot, Björn A1 - Eidner, Sascha A1 - Hess, Nancy J. A1 - Kaden, Peter A1 - Kremleva, Alena A1 - Kretzschmar, Jerome A1 - Krüger, Sven A1 - Platts, James A. A1 - Panak, Petra A1 - Polly, Robert A1 - Powell, Brian A. A1 - Rabung, Thomas A1 - Redon, Roland A1 - Reiller, Pascal E. A1 - Rösch, Notker A1 - Rossberg, André A1 - Scheinost, Andreas C. A1 - Schimmelpfennig, Bernd A1 - Schreckenbach, Georg A1 - Skerencak-Frech, Andrej A1 - Sladkov, Vladimir A1 - Solari, Pier Lorenzo A1 - Wang, Zheming A1 - Washton, Nancy M. A1 - Zhang, Xiaobin T1 - Interdisciplinary Round-Robin Test on molecular spectroscopy of the U(VI) Acetate System JF - ACS omega / American Chemical Society N2 - A comprehensive molecular analysis of a simple aqueous complexing system. U(VI) acetate. selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry. Y1 - 2019 U6 - https://doi.org/10.1021/acsomega.9b00164 SN - 2470-1343 VL - 4 IS - 5 SP - 8167 EP - 8177 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - López de Guereñu, Anna A1 - Bastian, Philipp A1 - Wessig, Pablo A1 - John, Leonard A1 - Kumke, Michael Uwe T1 - Energy Transfer between Tm-Doped Upconverting Nanoparticles and a Small Organic Dye with Large Stokes Shift JF - Biosensors : open access journal N2 - 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. KW - resonance energy transfer KW - DBD dye KW - core shell UCNP KW - time-resolved luminescence Y1 - 2019 U6 - https://doi.org/10.3390/bios9010009 SN - 2079-6374 VL - 9 IS - 1 PB - MDPI CY - Basel ER - TY - JOUR A1 - Haubitz, Toni A1 - John, Leonard A1 - Wessig, Pablo A1 - Kumke, Michael Uwe T1 - Photophysics of Acyl- and Ester-DBD Dyes BT - Quadrupole-Induced Solvent Relaxation Investigated by Transient Absorption Spectroscopy JF - the journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - A new generation of wavelength-tunable, fluorescent dyes, so-called DBD ([1,3]dioxolo[4,5-f][1,3]benzodioxole) dyes, were developed a few years ago, and they showed great potential as probes, for example, for fluorescence microscopy. However, their photophysics is not fully explored and leaves open questions regarding their large fluorescence Stokes shifts and sensitivity to solvent conditions of differently substituted DBD dyes. To improve the understanding of the influence of the substitution pattern of the DBD dyes on their respective photophysics, transient absorption spectroscopy (TAS) was used, that is, a pump-probe experiment on the femtosecond timescale. TAS allows measurements of excited states, ground state recovery, solvent relaxation, and fluorescence properties on time scales of up to several nanoseconds. Two different DBD dye samples were investigated: aryl- and ester-substituted DBD dyes. Experiments were carried out in solvents with different polarities using different excitation energies and at different viscosities. Based on the experimental data and theoretical calculations, we were able to determine the conformational changes of the molecule due to electronic excitation and were able to investigate solvent relaxation processes for both types of DBD dyes. By generalizing the theory for quadrupole-induced solvent relaxation developed by Togashi et al., we derived quadrupole moments of both molecules in the ground and excited state. Our data showed differences in the binding of polar solvent molecules to the dyes depending on the substituent on the DBD dye. In the case of water as the solvent, an additional efficient quenching process in the electronically excited state was revealed, which was indicated by the observation of solvated electrons in the TAS signals. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpca.9b02973 SN - 1089-5639 VL - 123 IS - 22 SP - 4717 EP - 4726 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - López de Guereñu Kurganova, Anna A1 - Klier, Dennis Tobias A1 - Haubitz, Toni A1 - Kumke, Michael Uwe T1 - Influence of Gd3+ doping concentration on the properties of Na(Y,Gd)F-4 BT - Yb3+, Tm3+ upconverting nanoparticles and their long-term aging behavior JF - Photochemical & photobiological sciences / European Society for Photobiology N2 - We present a systematic study on the properties of Na(Y,Gd)F-4-based upconverting nanoparticles (UCNP) doped with 18% Yb3+, 2% Tm3+, and the influence of Gd3+ (10-50 mol% Gd3+). UCNP were synthesized via the solvothermal method and had a range of diameters within 13 and 50 nm. Structural and photophysical changes were monitored for the UCNP samples after a 24-month incubation period in dry phase and further redispersion. Structural characterization was performed by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) as well as dynamic light scattering (DLS), and the upconversion luminescence (UCL) studies were executed at various temperatures (from 4 to 295 K) using time-resolved and steady-state spectroscopy. An increase in the hexagonal lattice phase with the increase of Gd3+ content was found, although the cubic phase was prevalent in most samples. The Tm3+-luminescence intensity as well as the Tm3+-luminescence decay times peaked at the Gd3+ concentration of 30 mol%. Although the general upconverting luminescence properties of the nanoparticles were preserved, the 24-month incubation period lead to irreversible agglomeration of the UCNP and changes in luminescence band ratios and lifetimes. KW - Upconversion luminescence KW - Lanthanides KW - Near infra-red KW - Ultra-low KW - temperature KW - Time-resolved spectroscopy Y1 - 2022 U6 - https://doi.org/10.1007/s43630-021-00161-4 SN - 1474-905X SN - 1474-9092 VL - 21 IS - 2 SP - 235 EP - 245 PB - Springer CY - Heidelberg ER - TY - GEN A1 - Kumke, Michael Uwe A1 - Eidner, Sascha T1 - Fluorescence and energy transfer processes of humic substances and related model compounds in terbium complexes N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 10 Y1 - 2005 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12255 ER - TY - GEN A1 - Burek, Katja A1 - Dengler, Joachim A1 - Emmerling, Franziska A1 - Feldmann, Ines A1 - Kumke, Michael Uwe A1 - Stroh, Julia T1 - Lanthanide Luminescence Revealing the Phase Composition in Hydrating Cementitious Systems T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The hydration process of Portland cement in a cementitious system is crucial for development of the high‐quality cement‐based construction material. Complementary experiments of X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM) and time‐resolved laser fluorescence spectroscopy (TRLFS) using europium (Eu(III)) as an optical probe are used to analyse the hydration process of two cement systems in the absence and presence of different organic admixtures. We show that different analysed admixtures and the used sulphate carriers in each cement system have a significant influence on the hydration process, namely on the time‐dependence in the formation of different hydrate phases of cement. Moreover, the effect of a particular admixture is related to the type of sulphate carrier used. The quantitative information on the amounts of the crystalline cement paste components is accessible via XRD analysis. Distinctly different morphologies of ettringite and calcium−silicate−hydrates (C−S−H) determined by SEM allow visual conclusions about formation of these phases at particular ageing times. The TRLFS data provides information about the admixture influence on the course of the silicate reaction. The dip in the dependence of the luminescence decay times on the hydration time indicates the change in the structure of C−S−H in the early hydration period. Complementary information from XRD, SEM and TRLFS provides detailed information on distinct periods of the cement hydration process. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 808 KW - cement admixtures KW - cement hydration KW - Europium KW - luminescence KW - SEM KW - X-ray diffraction Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-442433 SN - 1866-8372 IS - 808 ER - TY - JOUR A1 - Burek, Katja A1 - Dengler, Joachim A1 - Emmerling, Franziska A1 - Feldmann, Ines A1 - Kumke, Michael Uwe A1 - Stroh, Julia T1 - Lanthanide Luminescence Revealing the Phase Composition in Hydrating Cementitious Systems JF - ChemistryOpen N2 - The hydration process of Portland cement in a cementitious system is crucial for development of the high‐quality cement‐based construction material. Complementary experiments of X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM) and time‐resolved laser fluorescence spectroscopy (TRLFS) using europium (Eu(III)) as an optical probe are used to analyse the hydration process of two cement systems in the absence and presence of different organic admixtures. We show that different analysed admixtures and the used sulphate carriers in each cement system have a significant influence on the hydration process, namely on the time‐dependence in the formation of different hydrate phases of cement. Moreover, the effect of a particular admixture is related to the type of sulphate carrier used. The quantitative information on the amounts of the crystalline cement paste components is accessible via XRD analysis. Distinctly different morphologies of ettringite and calcium−silicate−hydrates (C−S−H) determined by SEM allow visual conclusions about formation of these phases at particular ageing times. The TRLFS data provides information about the admixture influence on the course of the silicate reaction. The dip in the dependence of the luminescence decay times on the hydration time indicates the change in the structure of C−S−H in the early hydration period. Complementary information from XRD, SEM and TRLFS provides detailed information on distinct periods of the cement hydration process. KW - cement admixtures KW - cement hydration KW - Europium KW - luminescence KW - SEM KW - X-ray diffraction Y1 - 2019 U6 - https://doi.org/10.1002/open.201900249 SN - 2191-1363 VL - 8 IS - 12 SP - 1441 EP - 1452 PB - Wiley-VCH-Verl. CY - Weinheim ER - TY - JOUR A1 - Schwarze, Thomas A1 - Müller, Holger A1 - Ast, Sandra A1 - Steinbrück, Dörte A1 - Eidner, Sascha A1 - Geißler, Felix A1 - Kumke, Michael Uwe A1 - Holdt, Hans-Jürgen ED - Kumke, Michael Uwe T1 - Fluorescence lifetime-based sensing of sodium by an optode JF - Chemical Communications N2 - We report a 1,2,3-triazol fluoroionophore for detecting Na+ that shows in vitro enhancement in the Na+-induced fluorescence intensity and decay time. The Na+-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na+ in the range of 1–10 mM by measuring reversible fluorescence decay time changes. KW - ion optodes KW - sensors KW - indicators KW - chromoionophore KW - ionophore KW - membrane KW - switches KW - systems KW - samples KW - green Y1 - 2014 SN - 0022-4936 SN - 0009-241X SP - 14167 EP - 14170 PB - The Royal Society Chemistry CY - Cambridge ER - TY - JOUR A1 - Schwarze, Thomas A1 - Mueller, Holger A1 - Ast, Sandra A1 - Steinbrück, Dorte A1 - Eidner, Sascha A1 - Geißler, Felix A1 - Kumke, Michael Uwe A1 - Holdt, Hans-Jürgen T1 - Fluorescence lifetime-based sensing of sodium by an optode JF - Chemical communications N2 - We report a 1,2,3-triazol fluoroionophore for detecting Na+ that shows in vitro enhancement in the Na+-induced fluorescence intensity and decay time. The Na+-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na+ in the range of 1-10 mM by measuring reversible fluorescence decay time changes. Y1 - 2014 U6 - https://doi.org/10.1039/c4cc06112h SN - 1359-7345 SN - 1364-548X VL - 50 IS - 91 SP - 14167 EP - 14170 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Schwarze, Thomas A1 - Müller, Holger A1 - Ast, Sandra A1 - Steinbrück, Dörte A1 - Eidner, Sascha A1 - Geißler, Felix A1 - Kumke, Michael Uwe A1 - Holdt, Hans-Jürgen T1 - Fluorescence lifetime-based sensing of sodium by an optode N2 - We report a 1,2,3-triazol fluoroionophore for detecting Na+ that shows in vitro enhancement in the Na+-induced fluorescence intensity and decay time. The Na+-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na+ in the range of 1–10 mM by measuring reversible fluorescence decay time changes. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 182 KW - ion optodes KW - sensors KW - indicators KW - chromoionophore KW - ionophore KW - membrane KW - switches KW - systems KW - samples KW - green Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-76785 SP - 14167 EP - 14170 PB - The Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Bastian, Philipp U. A1 - Yu, Leixiao A1 - de Guereñu Kurganova, Anna Lopez A1 - Haag, Rainer A1 - Kumke, Michael Uwe T1 - Bioinspired confinement of upconversion nanoparticles for improved performance in aqueous solution JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - The resonance energy transfer (RET) from NaYF4:Yb,Er upconverting nanoparticles (UNCPs) to a dye (5-carboxytetramethylrhodamine (TAMRA)) was investigated by photoluminescence experiments and microscale thermophoresis (MST). The dye was excited via RET from the UCNPs which was excited in the near-infrared (NIR). The change of the dye diffusion speed (free vs coupled) was investigated by MST. RET shows significant changes in the decay times of the dye as well as of the UCNPs. MST reveals significant changes in the diffusion speed. A unique amphiphilic coating polymer (customized mussel protein (CMP) polymer) for UCNP surface coating was used, which mimics blood protein adsorption and mussel food protein adhesion to transfer the UCNP into the aqueous phase and to allow surface functionalization. The CMP provides very good water dispersibility to the UCNPs and minimizes ligand exchange and subsequent UCNP aging reactions because of the interlinkage of the CMP on the UCNP surface. Moreover, CMP provides N-3-functional groups for dick chemistry-based functionalization demonstrated with the dye 5-carboxytetramethylrhodamine (TAMRA). This establishes the principle coupling scheme for suitable biomarkers such as antibodies. The CMP provides very stable aqueous UCNP dispersions that are storable up to 3 years in a fridge at 5 degrees C without dissolution or coagulation. The outstanding properties of CMP in shielding the UCNP from unwanted solvent effects is reflected in the distinct increase of the photoluminescence decay times after UCNP functionalization. The UCNP-to-TAMRA energy transfer is also spectroscopically investigated at low temperatures (4-200 K), revealing that one of the two green Er(III) emission bands contributes the major part to the energy transfer. The TAMRA fluorescence decay time increases by a factor of 9500 from 2.28 ns up to 22 mu s due to radiationless energy transfer from the UCNP after NIR excitation of the latter. This underlines the unique properties of CMP as a versatile capping ligand for distinctly improving the UCNPs' performance in aqueous solutions, for coupling of biomolecules, and for applications for in vitro and in vivo experiments using UCNPs as optical probes in life science applications. Y1 - 2020 U6 - https://doi.org/10.1021/acs.jpcc.0c09798 SN - 1932-7447 SN - 1932-7455 VL - 124 IS - 52 SP - 28623 EP - 28635 PB - American Chemical Society CY - Washington, DC ER - TY - JOUR A1 - Burek, Katja A1 - Krause, Felix A1 - Schwotzer, Matthias A1 - Nefedov, Alexei A1 - Süssmuth, Julia A1 - Haubitz, Toni A1 - Kumke, Michael Uwe A1 - Thissen, Peter T1 - Hydrophobic Properties of Calcium-Silicate Hydrates Doped with Rare-Earth Elements JF - ACS sustainable chemistry & engineering N2 - In this study, the apparent relationship between the transport process and the surface chemistry of the Calcium-Silicate Hydrate (CSH) phases was investigated. For this purpose, a method was developed to synthesize ultrathin CSH phases to be used as a model substrate with the specific modification of their structure by introducing europium (Eu(III)). The structural and chemical changes during this Eu(III)-doping were observed by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and time-resolved laser fluorescence spectroscopy (TRLFS). These alterations of the CSH phases led to significant changes in the surface chemistry and consequently to considerable variations in the interaction with water, as evidenced by measurements of the contact angles on the modified model substrates. Our results provide the basis for a more profound molecular understanding of reactive transport processes in cement-based systems. Furthermore, these results broaden the perspective of improving the stability of cement-based materials, which are subjected to the impact of aggressive aqueous environments through targeted modifications of the CSH phases. KW - Rare-earth elements KW - Europium KW - Luminescence KW - Metal-proton exchange reaction KW - Contact angle KW - Infrared spectroscopy KW - X-ray photoelectron spectroscopy Y1 - 2018 U6 - https://doi.org/10.1021/acssuschemeng.8b03244 SN - 2168-0485 VL - 6 IS - 11 SP - 14669 EP - 14678 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Luschtinetz, Franziska A1 - Dosche, Carsten A1 - Kumke, Michael Uwe T1 - Influence of streptavidin on the absorption and fluorescence properties of cyanine dyes N2 - Cyanine dyes have become widely used fluorescence labels in clinical and biological chemistry. In particular, cyanine dyes with excitation wavelengths lambda(ex) > 600 nm are often used in biological applications. However, aggregation behavior and matrix effects on cyanine fluorescence are not fully understood yet and interfere with the data interpretation. In this study, we analyzed the spectroscopic characteristics of a model system consisting of the biotinylated cyanine dyes DY-635 and DY-647 and their streptavidin conjugates. On the basis of the spectroscopic data, the interaction processes between cyanine dye molecules and proteins are discussed. Binding to streptavidin had a significant influence on both fluorescence and anisotropy decays of the cyanine dyes investigated. In particular, the fluorescence anisotropy was significantly altered, making it a promising detection parameter for bioanalytical applications in connection with the cyanine dyes used in the present study. In order to evaluate the time-resolved anisotropy, the introduction of a sophisticated kinetic model was required to describe the contributions from different fluorescing species properly. The rotational motion of streptavidin-bound dyes was analyzed using the associated anisotropy model, which allowed discrimination between contributions from different microenvironments. The anisotropy decay times increased by a factor of up to 20 due to protein binding. Y1 - 2009 UR - http://pubs.acs.org/journal/bcches U6 - https://doi.org/10.1021/Bc800497v SN - 1043-1802 ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Parvulescu, Vasile A1 - Parvulescu, Victoria A1 - Cotoi, Elena A1 - Gessner, Andre A1 - Kumke, Michael Uwe A1 - Simon, Simion A1 - Vasiliu, Florin T1 - Structural and photoluminescence characterization of mesoporous silicon-phosphates N2 - Two different types of mesoporous silicon-phosphate supports using different surfactants (a mixture of (CH3)(3)C13H27NBr with an organophosphorus coupling molecule (HO-PO(i-C3H7)(2)) and with a co-surfactant ((C2H5)(3)(C6H5)PCl), respectively) were synthesized. Trivalent europium (Eu) ions were immobilized via ion-exchange on these supports. The resulting materials were characterized using nitrogen adsorption isotherms at -196 degrees C, thermogravimetric analysis, SEM, TEM, FT-IR, PXRD, CP/MAS. (HSi)-H-1-Si-29 and P-31 NMR, DR-UV-vis as well as steady- state and time-resolved photoluminescence spectroscopy. The results evidenced that the co-polymerization of silicon and phosphorous yielded a unique morphology in these materials. Following calcination at 450 and 900 degrees C europium- exchanged silicon-phosphates with great surface area (BET=600-705 m(2) g(-1)) and 3.4 nm sized mesopores were obtained. The differences among the optical properties of the non-calcined europium materials such as the emission lifetimes, local environment at the europium sites or the relative contribution of the upper excited levels to the total photoluminescence were assigned to the surfactants used in the synthesis. Calcination of the silicon-phosphates at higher temperatures than 450 degrees C did not induce major changes in the structural properties: in contrast, photoluminescence properties of europium were markedly improved in terms of intensity and average lifetime. Y1 - 2010 UR - http://www.sciencedirect.com/science/journal/10106030 U6 - https://doi.org/10.1016/j.jphotochem.2010.07.015 SN - 1010-6030 ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Parvulescu, Vasile Ion A1 - Cojocaru, Bogdan A1 - Lorenz-Fonfria, Victor A. A1 - Kumke, Michael Uwe A1 - Gessner, Andre A1 - Enculescu, Ion T1 - Polymer-microporous host interactions probed by photoluminescence spectroscopy N2 - Zeolites NaY and ZSM-5 were used as hosts for styrene polymerization after ion-exchange with europium ions. The parent and hybrid, polystyrene coated Eu-NaY (Eu-NaY/PS) and Eu-ZSM-5 (Eu-ZSM-5/PS) zeolites were investigated by using thermal analysis, SEM, PXRD, FT-IR, DR-UV/Vis, steady state and time-resolved photoluminescence spectroscopy. FT-IR spectra evidenced for the interaction between the zeolitic hosts and polystyrene while the PXRD spectra supported for the presence of the polymer inside the channels/pores of Eu-NaY/PS and Eu-ZSM-5/PS materials. The optical properties of Eu-NaY/PS and Eu-ZSM-5/PS were significantly changed relative to those of the parent zeolites, giving further evidence for the presence of polymer inside zeolites. An interesting case is presented by NaY zeolite: following styrene polymerization, the polymer interacted selectively with one of the two main species co-existing inside zeolite while for ZSM-5 a similar effect was not observed. Y1 - 2010 UR - http://www.rsc.org/Publishing/Journals/CP/index.asp U6 - https://doi.org/10.1039/B922591a SN - 1463-9076 ER - TY - JOUR A1 - Marang, Laura A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Benedetti, Marc F. A1 - Reiller, Pascal E. T1 - Characterization of competitive binding of Eu(III)/Cu(II) and Eu(III)/Ca(II) to Gorleben humic acid Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/00167037 U6 - https://doi.org/10.1016/j.gca.2009.05.011 SN - 0016-7037 ER - TY - JOUR A1 - Marang, Laura A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Benedetti, Marc F. A1 - Reiller, Pascal E. T1 - Spectroscopic characterization of the competitive binding of Eu(III), Ca(II) and Cu(II) to a sedimentary originated humic acid N2 - The competition between REE, alkaline earth and d-transition metals for organic matter binding sites is still an open field of research; particularly, the mechanisms governing these phenomena need to be characterized in more detail. In this study, we examine spectroscopically the mechanisms of competitive binding of Eu(III)/Cu(II) and Eu(III)/ Ca(II) pair to Gorleben humic acid (HA), as previously proposed in the framework of the NICA-Donnan model. The evolution of time-resolved laser induced luminescence spectra of humic-complexed Eu(Ill) showed two strikingly different environments for a comparable bound proportion for Cu(II) and Ca(II). Cu(II) seems to compete more effectively with Eu(III) inducing its release into the Donnan phase, and into the bulk solution as free Eu3+. This is evidenced both by the shapes of the spectra and by the decrease in the luminescence decay times. In contrast with that, Ca(II) induces a modification of the HA structure, which enhances the luminescence of humic-bound Eu(III), and causes a minor modification of the chemical environment of the complexed rare earth ion. Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/00092541 U6 - https://doi.org/10.1016/j.chemgeo.2009.03.003 SN - 0009-2541 ER -