@article{AntoniouPashalidisGessneretal.2011, author = {Antoniou, Stella and Pashalidis, I. and Gessner, Andre and Kumke, Michael Uwe}, title = {The effect of humic acid on the formation and solubility of secondary solid phases (Nd(OH)CO3 and Sm(OH)CO3)}, series = {Radiochimica acta : international journal for chemical aspects of nuclear science and technology}, volume = {99}, journal = {Radiochimica acta : international journal for chemical aspects of nuclear science and technology}, number = {4}, publisher = {De Gruyter}, address = {Berlin}, issn = {0033-8230}, doi = {10.1524/ract.2011.1812}, pages = {217 -- 223}, year = {2011}, abstract = {The formation of secondary Ln(III) solid phases (e.g. Nd(OH)CO3 and Sm(OH)CO3) has been studied as a function of the humic acid (HA) concentration in 0.1 M NaClO4 aqueous solution and their solubility has been investigated in the neutral pH range (6.5-8) under normal atmospheric conditions. Nd(III) and Sm(III) were selected as analogues for trivalent lanthanide and actinide ions. The solid phases under investigation have been prepared by alkaline precipitation and characterized by TGA, ATR-FTIR, XRD, TRLFS, DR-UV-Vis and Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicate that Nd(OH)CO3 and Sm(OH)CO3 are stable and remain the solubility limiting solid phases even in the presence of increased HA concentration (0.5 g/L) in solution. Upon base addition in the Ln(III)-HA system decomplexation of the previously formed Ln(III)-humate complexes and precipitation of two distinct phases occurs, the inorganic (Ln(OH)CO3) and the organic phase (HA), which is adsorbed on the particle surface of the former. Nevertheless, HA affects the particle size of the solid phases. Increasing HA concentration results in decreasing crystallite size of the Nd(OH)CO3 and increasing crystallite size of the Sm(OH)CO3 solid phase, and affects inversely the solubility of the solid phases. However, this impact on the solid phase properties is expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.}, language = {en} } @article{AntoniouPashalidisGessneretal.2011, author = {Antoniou, Stella and Pashalidis, Ioannis and Gessner, Andre and Kumke, Michael Uwe}, title = {Spectroscopic investigations on the effect of humic acid on the formation and solubility of secondary solid phases of Ln(2)(CO3)(3)}, series = {Journal of rare earths}, volume = {29}, journal = {Journal of rare earths}, number = {6}, publisher = {Elsevier}, address = {Amsterdam}, issn = {1002-0721}, doi = {10.1016/S1002-0721(10)60490-5}, pages = {516 -- 521}, year = {2011}, abstract = {The formation of secondary Ln(III) solid phases (e.g., Nd-2(CO3)(3) and Sm-2(CO3)(3)) was studied as a function of the humic acid concentration in 0.1 mol/L NaClO4 aqueous solution in the neutral pH range (5-6.5). The solid phases under investigation were prepared by alkaline precipitation under 100\% CO2 atmosphere and characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), time-resolved laser fluorescence spectroscopy (TRLFS), diffuse reflectance ultraviolet-visible (DR-UV-Vis), Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicated that Nd-2(CO3)(3) and Sm-2(CO3)(3) were stable and remained the solubility limiting solid phases even in the presence of increased humic acid concentration (0.5 g/L) in solution. Upon base addition in the Ln(III)-HA system, decomplexation of the previously formed Ln(III)-humate complexes and precipitation of two distinct phases occurred, the inorganic (Ln(2)(CO3)(3)) and the organic phase (HA), which was adsorbed on the particle surface of the former. Nevertheless, humic acid affected the particle size of the solid phases. Increasing humic acid concentration resulted in decreasing crystallite size of the Nd-2(CO3)(3) and increasing crystallite size of the Sm-2(CO3)(3) solid phase, and affected inversely the solubility of the solid phases. However, this impact on the solid phase properties was expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.}, language = {en} } @article{KienzlerFlehrKrameretal.2011, author = {Kienzler, Andrea and Flehr, Roman and Kramer, Rolf A. and Gehne, Soeren and Kumke, Michael Uwe and Bannwarth, Willi}, title = {Novel Three-Color FRET Tool Box for Advanced Protein and DNA Analysis}, series = {Bioconjugate chemistry}, volume = {22}, journal = {Bioconjugate chemistry}, number = {9}, publisher = {American Chemical Society}, address = {Washington}, issn = {1043-1802}, doi = {10.1021/bc2002659}, pages = {1852 -- 1863}, year = {2011}, abstract = {We report on a new three-color FRET system which we were able to verify in peptides as well as in synthetic DNA. All three chromophores could be introduced by a building block approach avoiding postsynthetic labeling. Additional features are robustness, matching spectroscopic properties, high-energy transfer, and sensitivity. The system was investigated in detail on a set of peptides as well as an array of tailored oligonucleotides. The detailed analysis of the experimental data and comparison with theoretical considerations were in excellent agreement. It is shown that in the case of polypeptides specific interaction with the fluorescence probes has to be considered. In contrast with DNA, the fluorescence probes did not show any indications of such interactions. The novel three-color FRET toolbox revealed the potential for applications studying fundamental processes of three interacting molecules in life science applications.}, language = {en} } @article{KupstatKumkeHildebrandt2011, author = {Kupstat, Annette and Kumke, Michael Uwe and Hildebrandt, Niko}, title = {Toward sensitive, quantitative point-of-care testing (POCT) of protein markers miniaturization of a homogeneous time-resolved fluoroimmunoassay for prostate-specific antigen detection}, series = {The analyst : the analytical journal of the Royal Society of Chemistry}, volume = {136}, journal = {The analyst : the analytical journal of the Royal Society of Chemistry}, number = {5}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0003-2654}, doi = {10.1039/c0an00684j}, pages = {1029 -- 1035}, year = {2011}, abstract = {Point-of-care testing (POCT) systems which allow for a sensitive, quantitative detection of protein markers are extremely useful for the early detection and therapy progress monitoring of cancer. However, currently commercially available POCT devices are mainly limited to the qualitative detection of protein markers. In this study we demonstrate the successive miniaturization of a sensitive and fast assay for the quantitative detection of prostate-specific antigen (PSA) using a well established and clinically approved homogeneous time-resolved fluoroimmunoassay technology (TRACE (R)) on a commercial plate-reader system (KRYPTOR (R)). Regarding the initial requirements for the development of POCT devices we applied a 30-fold assay volume reduction (150 mu L to 5 mu L) to achieve a reasonable lab-on-a-chip volume and a 24-fold and 120-fold excitation pulse energy reduction to achieve reasonable pulse energies for low-cost miniature excitation sources. Due to highly efficient optimization of key POCT parameters our miniaturized PSA assay achieved a 30\% increased sensitivity and a 2-fold improved limit of detection compared to the standard plate-reader method. Our results demonstrate the successful implementation of key parameters for a significant miniaturization and for cost reduction in the clinically approved KRYPTOR (R) platform for protein detection. The technological alterations required are easy-to-implement and can be immediately adapted for more than 30 diagnostic protein markers already available for the KRYPTOR (R) platform. These features strongly recommend our assay format to be utilized in innovative, sensitive, quantitative POCT of protein markers.}, language = {en} } @article{KupstatRitschelKumke2011, author = {Kupstat, Annette and Ritschel, Thomas and Kumke, Michael Uwe}, title = {Oxazine Dye-Conjugated DNA Oligonucleotides Forster Resonance Energy Transfer in View of Molecular Dye-DNA Interactions}, series = {Bioconjugate chemistry}, volume = {22}, journal = {Bioconjugate chemistry}, number = {12}, publisher = {American Chemical Society}, address = {Washington}, issn = {1043-1802}, doi = {10.1021/bc200379y}, pages = {2546 -- 2557}, year = {2011}, abstract = {In this work, the photophysical properties of two oxazine dyes (ATTO 610 and ATTO 680) covalently attached via a C6-amino linker to the 5'-end of short single-stranded as well as double-stranded DNA (ssDNA and dsDNA, respectively) of different lengths were investigated. The two oxazine dyes were chosen because of the excellent spectral overlap, the high extinction coefficients, and the high fluorescence quantum yield of ATTO 610, making them an attractive Forster resonance energy transfer (FRET) pair for bioanalytical applications in the far-red spectral range. To identify possible molecular dye-DNA interactions that cause photophysical alterations, we performed a detailed spectroscopic study, including time-resolved fluorescence anisotropy and fluorescence correlation spectroscopy measurements. As an effect of the DNA conjugation, the absorption and fluorescence maxima of both dyes were bathochromically shifted and the fluorescence decay times were increased. Moreover, the absorption of conjugated ATTO 610 was spectrally broadened, and a dual fluorescence emission was observed. Steric interactions with ssDNA as well as dsDNA were found for both dyes. The dye-DNA interactions were strengthened from ssDNA to dsDNA conjugates, pointing toward interactions with specific dsDNA domains (such as the top of the double helix). Although these interactions partially blocked the dye-linker rotation, a free (unhindered) rotational mobility of at least one dye facilitated the appropriate alignment of the transition dipole moments in doubly labeled ATTO 610/ATTO 680-dsDNA conjugates for the performance of successful FRET. Considering the high linker flexibility for the determination of the donor-acceptor distances, good accordance between theoretical and experimental FRET parameters was obtained. The considerably large Forster distance of similar to 7 nm recommends the application of this FRET pair not only for the detection of binding reactions between nucleic acids in living cells but also for monitoring interactions of larger biomolecules such as proteins.}, language = {en} } @article{RadziukSkirtachGessneretal.2011, author = {Radziuk, Darya and Skirtach, Andre and Gessner, Andre and Kumke, Michael Uwe and Zhang, Wei and M{\"o}hwald, Helmuth and Shchukin, Dmitry}, title = {Ultrasonic Approach for Formation of Erbium Oxide Nanoparticles with Variable Geometries}, series = {Langmuir}, volume = {27}, journal = {Langmuir}, number = {23}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/la203622u}, pages = {14472 -- 14480}, year = {2011}, abstract = {Ultrasound (20 kHz, 29 W. cm(-2)) is employed to form three types of erbium oxide nanoparticles in the presence of multiwalled carbon nanotubes as a template material in water. The nanoparticles are (i) erbium carboxioxide nanoparticles deposited on the external walls of multiwalled carbon nanotubes and Er(2)O(3) in the bulk with (ii) hexagonal and (iii) spherical geometries. Each type of ultrasonically formed nanoparticle reveals Er(3+) photoluminescence from crystal lattice. The main advantage of the erbium carboxioxide nanoparticles on the carbon nanotubes is the electromagnetic emission in the visible region, which is new and not examined up to the present date. On the other hand, the photoluminescence of hexagonal erbium oxide nanoparticles is long-lived (mu s) and enables the higher energy transition ((4)S(3/2)-(4)I(15/2)), which is not observed for spherical nanoparticles. Our work is unique because it combines for the first time spectroscopy of Er(3+) electronic transitions in the host crystal lattices of nanoparticles with the geometry established by ultrasound in aqueous solution of carbon nanotubes employed as a template material. The work can be of great interest for "green" chemistry synthesis of photoluminescent nanoparticles in water.}, language = {en} }