@misc{TasiorBaldDeperasińskaetal.2015, author = {Tasior, Mariusz and Bald, Ilko and Deperasińska, Irena and Cywiński, Piotr J. and Gryko, Daniel T.}, title = {An internal charge transfer-dependent solvent effect in V-shaped azacyanines}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102704}, pages = {11714 -- 11720}, year = {2015}, abstract = {New V-shaped non-centrosymmetric dyes, possessing a strongly electron-deficient azacyanine core, have been synthesized based on a straightforward two-step approach. The key step in this synthesis involves palladium-catalysed cross-coupling of dibromo-N,N′-methylene-2,2′-azapyridinocyanines with arylacetylenes. The resulting strongly polarized π-expanded heterocycles exhibit green to orange fluorescence and they strongly respond to changes in solvent polarity. We demonstrate that differently electron-donating peripheral groups have a significant influence on the internal charge transfer, hence on the solvent effect and fluorescence quantum yield. TD-DFT calculations confirm that, in contrast to the previously studied bis(styryl)azacyanines, the proximity of S1 and T2 states calculated for compounds bearing two 4-N,N-dimethylaminophenylethynyl moieties establishes good conditions for efficient intersystem crossing and is responsible for its low fluorescence quantum yield. Non-linear properties have also been determined for new azacyanines and the results show that depending on peripheral groups, the synthesized dyes exhibit small to large two-photon absorption cross sections reaching 4000 GM.}, language = {en} } @article{OlejkoCywinskiBald2015, author = {Olejko, Lydia and Cywinski, Piotr J. and Bald, Ilko}, title = {Ion-Selective formation of a guanine quadruplex on DNA origami structures}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {2}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201409278}, pages = {673 -- 677}, year = {2015}, abstract = {DNA origami nanostructures are a versatile tool that can be used to arrange functionalities with high local control to study molecular processes at a single-molecule level. Here, we demonstrate that DNA origami substrates can be used to suppress the formation of specific guanine (G) quadruplex structures from telomeric DNA. The folding of telomeres into G-quadruplex structures in the presence of monovalent cations (e.g. Na+ and K+) is currently used for the detection of K+ ions, however, with insufficient selectivity towards Na+. By means of FRET between two suitable dyes attached to the 3- and 5-ends of telomeric DNA we demonstrate that the formation of G-quadruplexes on DNA origami templates in the presence of sodium ions is suppressed due to steric hindrance. Hence, telomeric DNA attached to DNA origami structures represents a highly sensitive and selective detection tool for potassium ions even in the presence of high concentrations of sodium ions.}, language = {en} } @article{TasiorBaldDeperasinskaetal.2015, author = {Tasior, Mariusz and Bald, Ilko and Deperasinska, Irena and Cywinski, Piotr J. and Gryko, Daniel T.}, title = {An internal charge transfer-dependent solvent effect in V-shaped azacyanines}, series = {Organic \& biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry}, volume = {13}, journal = {Organic \& biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry}, number = {48}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-0520}, doi = {10.1039/c5ob01633a}, pages = {11714 -- 11720}, year = {2015}, language = {en} } @article{MeilingCywinskiBald2016, author = {Meiling, Till T. and Cywinski, Piotr J. and Bald, Ilko}, title = {White carbon: Fluorescent carbon nanoparticles with tunable quantum yield in a reproducible green synthesis}, series = {Scientific reports}, volume = {6}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/srep28557}, pages = {9}, year = {2016}, abstract = {In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (> 1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1\% up to 28\% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.}, language = {en} } @article{MeilingCywińskiBald2016, author = {Meiling, Till Thomas and Cywiński, Piotr J. and Bald, Ilko}, title = {White carbon: Fluorescent carbon nanoparticles with tunable quantum yield in a reproducible green synthesis}, series = {Scientific reports}, volume = {6}, journal = {Scientific reports}, publisher = {Nature Publishing Group}, address = {London}, doi = {10.1038/srep28557}, pages = {9}, year = {2016}, abstract = {In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (>1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1\% up to 28\% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.}, language = {en} } @article{OlejkoCywińskiBald2016, author = {Olejko, Lydia and Cywiński, Piotr J. and Bald, Ilko}, title = {An ion-controlled four-color fluorescent telomeric switch on DNA origami structures}, series = {Nanoscale}, volume = {8}, journal = {Nanoscale}, publisher = {RSC Publ.}, address = {Cambridge}, issn = {2040-3372}, doi = {10.1039/C6NR00119J}, pages = {10339 -- 10347}, year = {2016}, abstract = {The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using F{\"o}rster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.}, language = {en} } @article{HarmaPihlasaloCywinskietal.2013, author = {Harma, Harri and Pihlasalo, Sari and Cywinski, Piotr J. and Mikkonen, Piia and Hammann, Tommy and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Hanninen, Pekka}, title = {Protein quantification using resonance energy transfer between donor nanoparticles and acceptor quantum dots}, series = {Analytical chemistry}, volume = {85}, journal = {Analytical chemistry}, number = {5}, publisher = {American Chemical Society}, address = {Washington}, issn = {0003-2700}, doi = {10.1021/ac303586n}, pages = {2921 -- 2926}, year = {2013}, abstract = {A homogeneous time-resolved luminescence resonance energy transfer (TR-LRET) assay has been developed to quantify proteins. The competitive assay is based on resonance energy transfer (RET) between two luminescent nanosized particles. Polystyrene nanoparticles loaded with Eu3+ chelates (EuNPs) act as donors, while protein-coated quantum dots (QDs), either CdSe/ZnS emitting at 655 nm (QD655-strep) or CdSeTe/ZnS with emission wavelength at 705 nm (QD705-strep), are acceptors. In the absence of analyte protein, in our case bovine serum albumin (BSA), the protein-coated QDs bind nonspecifically to the EuNPs, leading to RET. In the presence of analyte proteins, the binding of the QDs to the EuNPs is prevented and the RET signal decreases. RET from the EuNPs to the QDs was confirmed and characterized with steady-state and time-resolved luminescence spectroscopy. In accordance with the Forster theory, the approximate average donor acceptor distance is around 15 nm at RET efficiencies, equal to 15\% for QD655 and 13\% for QD705 acceptor, respectively. The limits of detection are below 10 ng of BSA with less than a 10\% average coefficient of variation. The assay sensitivity is improved, when compared to the most sensitive commercial methods. The presented mix-and-measure method has potential to be implemented into routine protein quantification in biological laboratories.}, language = {en} } @article{WeclawskiMeilingLeniaketal.2015, author = {Weclawski, Marek K. and Meiling, Till Thomas and Leniak, Arkadiusz and Cywinski, Piotr J. and Gryko, Daniel T.}, title = {Planar, Fluorescent Push-Pull System That Comprises Benzofuran and Iminocoumarin Moieties}, series = {Organic letters}, volume = {17}, journal = {Organic letters}, number = {17}, publisher = {American Chemical Society}, address = {Washington}, issn = {1523-7060}, doi = {10.1021/acs.orglett.5b02042}, pages = {4252 -- 4255}, year = {2015}, abstract = {Previously unknown, vertically linked heterocycles comprised of benzofuran and iminocoumarin moieties have been synthesized directly from 1,5-dibenzoyloxyanthraquinone and arylacetonitriles via double Knoevenagel condensation followed by formal HCN elimination. The structural assembly of fully conjugated, electron-rich benzofuran and electron-deficient iminocoumarin is responsible for the strongly polarized nature of these heterocycles which translates into their polarity-sensitive fluorescence.}, language = {en} } @article{NazirMeilingCywinskietal.2015, author = {Nazir, Rashid and Meiling, Till Thomas and Cywinski, Piotr J. and Gryko, Daniel T.}, title = {Synthesis and Optical Properties of alpha,beta-Unsaturated Ketones Bearing a Benzofuran Moiety}, series = {Asian journal of organic chemistry : an ACES journal}, volume = {4}, journal = {Asian journal of organic chemistry : an ACES journal}, number = {9}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2193-5807}, doi = {10.1002/ajoc.201500242}, pages = {929 -- 935}, year = {2015}, abstract = {Five pi-expanded alpha,beta-unsaturated ketones have been prepared from a strongly electron-rich benzofuran derivative via Knoevenagel reaction and aldol condensation. The incorporation of two 6-didodecylaminobenzofuran-2-yl groups at the periphery of D-pi-A and D-pi-A-pi-D molecules resulted in dyes with excellent solubility in the majority of organic solvents. In contrast to the majority of alpha,beta-unsaturated ketones, these dyes emit relatively strongly in the red region with a fluorescence quantum yield up to 40\%. They also display strong solvatofluorochromism with emission shifting from 570 nm in toluene to 670 nm in CHCl3. Depending on the chemical structure, they two-photon cross-sections (sigma(2)) are up to 1700 GM (1 GM=10(50) cm(4)s photon(-1)).}, language = {en} } @article{CywinskiOlejkoLoehmannsroeben2015, author = {Cywinski, Piotr J. and Olejko, Lydia and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {A time-resolved luminescent competitive assay to detect L-selectin using aptamers as recognition elements}, series = {Analytica chimica acta : an international journal devoted to all branches of analytical chemistry}, volume = {887}, journal = {Analytica chimica acta : an international journal devoted to all branches of analytical chemistry}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0003-2670}, doi = {10.1016/j.aca.2015.06.045}, pages = {209 -- 215}, year = {2015}, abstract = {L-selectin is a protein with potential importance for numerous diseases and clinical disorders. In this paper, we present a new aptamer-based luminescent assay developed to detect L-selectin. The sensing system working principle is based on Forster Resonance Energy Transfer (FRET) from a donor terbium complex (TbC) to an acceptor cyanine dye (Cy5). In the present approach, the biotinylated aptamer is combined with Cy5-labelled streptavidin (Cy5-Strep) to yield an aptamer-based acceptor construct (Apta-Cy5-Strep), while L-selectin is conjugated using luminescent TbC. Upon aptamer binding to the TbC-labelled L-selectin (L-selectin-TbC), permanent donor-acceptor proximity is established which allows for radiationless energy transfer to occur. However, when unlabelled L-selectin is added, it competes with the L-selectin-TbC and the FRET signal decreases as the L-selectin concentration increases. FRET from the TbC to Cy5 was observed with time-gated time-resolved luminescence spectroscopy. A significant change in the corrected luminescence signal was observed in the dynamic range of 10 -500 ng/mL L-selectin, the concentration range relevant for accelerated cognitive decline of Alzheimer's disease, with a limit of detection (LOD) equal to 10 ng/mL. The aptasensor-based assay is homogeneous and can be realized within one hour. Therefore, this method has the potential to become an alternative to tedious heterogeneous analytical methods, e.g. based on enzyme-linked immunosorbent assay (ELISA). (C) 2015 Elsevier B.V. All rights reserved.}, language = {en} }