TY - JOUR A1 - Fudickar, Werner A1 - Metz, Melanie A1 - Mai-Linde, Yasemin A1 - Krüger, Tobias A1 - Kelling, Alexandra A1 - Sperlich, Eric A1 - Linker, Torsten T1 - Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes JF - Photochemistry and photobiology : the official journal of the American Society for Photobiology N2 - The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions. Y1 - 2021 U6 - https://doi.org/10.1111/php.13422 SN - 0031-8655 SN - 1751-1097 VL - 97 IS - 6 SP - 1289 EP - 1297 PB - Wiley CY - Malden, Mass. ER - TY - JOUR A1 - Raju, Rajarshi Roy A1 - Koetz, Joachim T1 - Inner rotation of Pickering Janus emulsions JF - Nanomaterials : open access journal N2 - Janus droplets were prepared by vortex mixing of three non-mixable liquids, i.e., olive oil, silicone oil and water, in the presence of gold nanoparticles (AuNPs) in the aqueous phase and magnetite nanoparticles (MNPs) in the olive oil. The resulting Pickering emulsions were stabilized by a red-colored AuNP layer at the olive oil/water interface and MNPs at the oil/oil interface. The core–shell droplets can be stimulated by an external magnetic field. Surprisingly, an inner rotation of the silicon droplet is observed when MNPs are fixed at the inner silicon droplet interface. This is the first example of a controlled movement of the inner parts of complex double emulsions by magnetic manipulation via interfacially confined magnetic nanoparticles. KW - Janus droplets KW - Pickering emulsions KW - magnetic manipulation KW - gold nanoparticles KW - magnetite nanoparticles Y1 - 2021 U6 - https://doi.org/10.3390/nano11123312 SN - 2079-4991 VL - 11 IS - 12 PB - MDPI CY - Basel ER - TY - JOUR A1 - Picconi, David T1 - Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline JF - Photochemical & photobiological sciences N2 - The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi* excited states and a n pi* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time- resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1 pi pi* <- S-0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2 pi pi* <- S-0 excitation are instead nonadiabatic, and the n pi* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone.
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. KW - Excited state proton transfer KW - Quantum dynamics KW - Nonadiabatic effects KW - Spectroscopy KW - Coherences Y1 - 2021 U6 - https://doi.org/10.1007/s43630-021-00112-z SN - 1474-905X SN - 1474-9092 VL - 20 IS - 11 SP - 1455 EP - 1473 PB - Springer CY - Heidelberg ER - TY - THES A1 - Nacak, Selma T1 - Synthesis and Characterization of Upconversion Nanaparticles for Applications in Life Sciences Y1 - 2021 ER - TY - JOUR A1 - Neffe, Axel T. A1 - Izraylit, Victor A1 - Hommes-Schattmann, Paul J. A1 - Lendlein, Andreas T1 - Soft, formstable (Co)polyester blend elastomers JF - Nanomaterials : open access journal N2 - High crystallization rate and thermomechanical stability make polylactide stereocomplexes effective nanosized physical netpoints. Here, we address the need for soft, form-stable degradable elastomers for medical applications by designing such blends from (co)polyesters, whose mechanical properties are ruled by their nanodimensional architecture and which are applied as single components in implants. By careful controlling of the copolymer composition and sequence structure of poly[(L-lactide)-co-(epsilon-caprolactone)], it is possible to prepare hyperelastic polymer blends formed through stereocomplexation by adding poly(D-lactide) (PDLA). Low glass transition temperature T-g <= 0 degrees C of the mixed amorphous phase contributes to the low Young's modulus E. The formation of stereocomplexes is shown in DSC by melting transitions T-m > 190 degrees C and in WAXS by distinct scattering maxima at 2 theta = 12 degrees and 21 degrees. Tensile testing demonstrated that the blends are soft (E = 12-80 MPa) and show an excellent hyperelastic recovery R-rec = 66-85% while having high elongation at break epsilon(b) up to >1000%. These properties of the blends are attained only when the copolymer has 56-62 wt% lactide content, a weight average molar mass >140 kg center dot mol(-1), and number average lactide sequence length >= 4.8, while the blend is formed with a content of 5-10 wt% of PDLA. The devised strategy to identify a suitable copolymer for stereocomplexation and blend formation is transferable to further polymer systems and will support the development of thermoplastic elastomers suitable for medical applications. KW - thermoplastic elastomer KW - biomaterial KW - stereocomplexes KW - mechanical KW - properties KW - form stability KW - crystallinity Y1 - 2021 U6 - https://doi.org/10.3390/nano11061472 SN - 2079-4991 VL - 11 IS - 6 PB - MDPI CY - Basel ER - TY - JOUR A1 - Fudickar, Werner A1 - Roder, Phillip A1 - Listek, Martin A1 - Hanack, Katja A1 - Linker, Torsten T1 - Pyridinium alkynylanthracenes as sensitizers for photodynamic therapy JF - Photochemistry and photobiology N2 - Photodynamic therapy (PDT) is a mild but effective method to treat certain types of cancer upon irradiation with visible light. Here, three isomeric methylpyridinium alkynylanthracenes 1op were evaluated as sensitizers for PDT. Upon irradiation with blue or green light, all three compounds show the ability to initiate strand breaks of plasmid DNA. The mayor species responsible for cleavage is singlet oxygen (O-1(2)) as confirmed by scavenging reagents. Only isomers 1m and 1p can be incorporated into HeLa cells, whereas isomer 1o cannot permeate through the membrane. While isomer 1m targets the cell nucleus, isomer 1p assembles in the cellular cytoplasm and impacts the cellular integrity. This is in accordance with a moderate toxicity of 1p in the dark, whereas 1m exhibits no dark toxicity. Both isomers are suitable as PDT reagents, with a CC50 of 3 mu m and 75 nm, for 1p and 1m, respectively. Thus, derivative 1m, which can be easily synthesized, becomes an interesting candidate for cancer therapy. Y1 - 2021 U6 - https://doi.org/10.1111/php.13554 SN - 0031-8655 SN - 1751-1097 VL - 98 IS - 1 SP - 193 EP - 201 PB - Wiley CY - Hoboken ER - TY - CHAP A1 - Ramadan, Shahenda A1 - Guerrero, Paula A1 - Nedielkov, Ruslan A1 - Klishin, Nikolai A1 - Dimova, Rumiana A1 - Silva, Daniel V. A1 - Möller, Heiko T1 - Building a mimetic system for unraveling protein-protein interactions on membranes T2 - European biophysics journal : with biophysics letters ; an international journal of biophysics Y1 - 2021 U6 - https://doi.org/10.1007/s00249-021-01558-w SN - 0175-7571 SN - 1432-1017 VL - 50 IS - SUPPL 1 SP - S153 EP - S153 PB - Springer CY - Berlin ; Heidelberg ; New York ER - TY - JOUR A1 - Neffe, Axel T. A1 - Löwenberg, Candy A1 - Julich-Gruner, Konstanze K. A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Thermally-induced shape-memory behavior of degradable gelatin-based networks JF - International journal of molecular sciences N2 - Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) alpha,omega-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27-23 kPa and Young's moduli of 215-360 kPa at 4 degrees C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 degrees C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates R-r close to 100% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix. KW - shape-memory hydrogel KW - active polymer KW - biopolymer KW - mechanical KW - properties KW - degradation Y1 - 2021 U6 - https://doi.org/10.3390/ijms22115892 SN - 1422-0067 SN - 1661-6596 VL - 22 IS - 11 PB - Molecular Diversity Preservation International CY - Basel ER - TY - JOUR A1 - Bastian, Philipp U. A1 - Robel, Nathalie A1 - Schmidt, Peter A1 - Schrumpf, Tim A1 - Günter, Christina A1 - Roddatis, Vladimir A1 - Kumke, Michael U. T1 - Resonance energy transfer to track the motion of lanthanide ions BT - what drives the intermixing in core-shell upconverting nanoparticles? JF - Biosensors : open access journal N2 - The imagination of clearly separated core-shell structures is already outdated by the fact, that the nanoparticle core-shell structures remain in terms of efficiency behind their respective bulk material due to intermixing between core and shell dopant ions. In order to optimize the photoluminescence of core-shell UCNP the intermixing should be as small as possible and therefore, key parameters of this process need to be identified. In the present work the Ln(III) ion migration in the host lattices NaYF4 and NaGdF4 was monitored. These investigations have been performed by laser spectroscopy with help of lanthanide resonance energy transfer (LRET) between Eu(III) as donor and Pr(III) or Nd(III) as acceptor. The LRET is evaluated based on the Forster theory. The findings corroborate the literature and point out the migration of ions in the host lattices. Based on the introduced LRET model, the acceptor concentration in the surrounding of one donor depends clearly on the design of the applied core-shell-shell nanoparticles. In general, thinner intermediate insulating shells lead to higher acceptor concentration, stronger quenching of the Eu(III) donor and subsequently stronger sensitization of the Pr(III) or the Nd(III) acceptors. The choice of the host lattice as well as of the synthesis temperature are parameters to be considered for the intermixing process. KW - upconversion nanoparticles KW - lanthanoid migration KW - lanthanides KW - core-shell KW - energy transfer Y1 - 2021 U6 - https://doi.org/10.3390/bios11120515 SN - 2079-6374 VL - 11 IS - 12 PB - MDPI CY - Basel ER - TY - JOUR A1 - Lau, Skadi A1 - Maier, Anna A1 - Braune, Steffen A1 - Gossen, Manfred A1 - Lendlein, Andreas T1 - Effect of endothelial culture medium composition on platelet responses to polymeric biomaterials JF - International journal of molecular sciences N2 - Near-physiological in vitro thrombogenicity test systems for the evaluation of blood-contacting endothelialized biomaterials requires co-cultivation with platelets (PLT). However, the addition of PLT has led to unphysiological endothelial cell (EC) detachment in such in vitro systems. A possible cause for this phenomenon may be PLT activation triggered by the applied endothelial cell medium, which typically consists of basal medium (BM) and nine different supplements. To verify this hypothesis, the influence of BM and its supplements was systematically analyzed regarding PLT responses. For this, human platelet rich plasma (PRP) was mixed with BM, BM containing one of nine supplements, or with BM containing all supplements together. PLT adherence analysis was carried out in six-channel slides with plasma-treated cyclic olefin copolymer (COC) and poly(tetrafluoro ethylene) (PTFE, as a positive control) substrates as part of the six-channel slides in the absence of EC and under static conditions. PLT activation and aggregation were analyzed using light transmission aggregometry and flow cytometry (CD62P). Medium supplements had no effect on PLT activation and aggregation. In contrast, supplements differentially affected PLT adherence, however, in a polymer- and donor-dependent manner. Thus, the use of standard endothelial growth medium (BM + all supplements) maintains functionality of PLT under EC compatible conditions without masking the differences of PLT adherence on different polymeric substrates. These findings are important prerequisites for the establishment of a near-physiological in vitro thrombogenicity test system assessing polymer-based cardiovascular implant materials in contact with EC and PLT. KW - cyclic olefin copolymer KW - poly(tetrafluoroethylene) KW - endothelial cells KW - platelets KW - in vitro thrombogenicity testing Y1 - 2021 U6 - https://doi.org/10.3390/ijms22137006 SN - 1422-0067 SN - 1661-6596 VL - 22 IS - 13 PB - Molecular Diversity Preservation International CY - Basel ER -