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Author: Then, Patrick × Publisher: Weinheim : Wiley-VCH ×

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    PEGylation of Guanidinium and Indole Bearing Poly(methacrylamide)s - Biocompatible Terpolymers for pDNA Delivery
    (Weinheim : Wiley-VCH, 2021) Cokca, Ceren; Hack, Franz J.; Costabel, Daniel; Herwig, Kira; Hülsmann, Juliana; Then, Patrick; Heintzmann, Rainer; Fischer, Dagmar; Peneva, Kalina
    This study describes the first example for shielding of a high performing terpolymer that consists of N-(2-hydroxypropyl)methacrylamide (HPMA), N-(3-guanidinopropyl)methacrylamide (GPMA), and N-(2-indolethyl)methacrylamide monomers (IEMA) by block copolymerization of a polyethylene glycol derivative – poly(nona(ethylene glycol)methyl ether methacrylate) (P(MEO9MA)) via reversible addition–fragmentation chain transfer (RAFT) polymerization. The molecular weight of P(MEO9MA) is varied from 3 to 40 kg mol–1 while the comonomer content of HPMA, GPMA, and IEMA is kept comparable. The influence of P(MEO9MA) block with various molecular weights is investigated over cytotoxicity, plasmid DNA (pDNA) binding, and transfection efficiency of the resulting polyplexes. Overall, the increase in molecular weight of P(MEO9MA) block demonstrates excellent biocompatibility with higher cell viability in L-929 cells and an efficient binding to pDNA at N/P ratio of 2. The significant transfection efficiency in CHO-K1 cells at N/P ratio 20 is obtained for block copolymers with molecular weight of P(MEO9MA) up to 10 kg mol–1. Moreover, a fluorescently labeled analogue of P(MEO9MA), bearing perylene monoimide methacrylamide (PMIM), is introduced as a comonomer in RAFT polymerization. Polyplexes consisting of labeled block copolymer with 20 kg mol–1 of P(MEO9MA) and pDNA are incubated in Hela cells and investigated through structured illumination microscopy (SIM).
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    Excited-State Dynamics in Borylated Arylisoquinoline Complexes in Solution and in cellulo
    (Weinheim : Wiley-VCH, 2023) Yang, Tingxiang; Valavalkar, Abha; Romero‐Arenas, Antonio; Dasgupta, Anindita; Then, Patrick; Chettri, Avinash; Eggeling, Christian; Ros, Abel; Pischel, Uwe; Dietzek‐Ivanšić, Benjamin
    Two four-coordinate organoboron N,C-chelate complexes with different functional terminals on the PEG chains are studied with respect to their photophysical properties within human MCF-7 cells. Their excited-state properties are characterized by time-resolved pump-probe spectroscopy and fluorescence lifetime microscopy. The excited-state relaxation dynamics of the two complexes are similar when studied in DMSO. Aggregation of the complexes with the carboxylate terminal group is observed in water. When studying the light-driven excited-state dynamics of both complexes in cellulo, i. e., after being taken up into human MCF-7 cells, both complexes show different features depending on the nature of the anchoring PEG chains. The lifetime of a characteristic intramolecular charge-transfer state is significantly shorter when studied in cellulo (360±170 ps) as compared to in DMSO (∼960 ps) at 600 nm for the complexes with an amino group. However, the kinetics of the complexes with the carboxylate group are in line with those recorded in DMSO. On the other hand, the lifetimes of the fluorescent state are almost identical for both complexes in cellulo. These findings underline the importance to evaluate the excited-state properties of fluorophores in a complex biological environment in order to fully account for intra- and intermolecular effects governing the light-induced processes in functional dyes.