Aromatic, microporous polymer networks with high surface area generated in Friedel-Crafts-type polycondensations

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.A series of novel, microporous polymer networks (MPNs) have been generated in a simple, acid catalysed Friedel–Crafts-type self-condensation of A2B2- and A2B4-type fluorenone monomers. Two A2B4-type monomers with 2,7-bis(N,N-diphenylamino) A or 2,7-bis[4-(N,N-diphenylamino)phenyl] D substitution of the fluorenone cores lead to MPNs with high SBET surface areas of up to 1400 m2 g−1. Two MPNs made of binary monomer mixtures showed the highest Brunauer–Emmett–Teller (BET) surface areas SBET of our series (SBET of up to 1800 m2 g−1) after washing the powdery samples with supercritical carbon dioxide. Total pore volumes of up to 1.6 cm3 g−1 have been detected. It is observed that the substitution pattern of the monomers is strongly influencing the resulting physicochemical properties of the microporous polymer networks (MPNs)

Aromatic polymers made by reductive polydehalogenation of oligocyclic monomers as conjugated polymers of intrinsic microporosity (C-PIMs)

Reductive dehalogenation polycondensation of a series of penta-or hexacyclic, bisgeminal tetrachlorides with dicobalt octacarbonyl leads to the formation of homopolymers and copolymers with very different optical spectra. While the formation of tetrabenzoheptafulvalene connectors introduces efficient conjugation barriers due to their strongly folded structure, linking of 5-membered ring-based pentacyclic building blocks via bifluorenylidene connectors allows for an extended π-conjugation along the main chain. A comparison of homopolymer P57 and copolymer P55/77 indicates a quite different reactivity for dichloromethylene functions if incorporated into 5-or 7-membered rings. Interestingly, all investigated (co)polymers show an intrinsic microporosity in the solid-state (forming so-called Conjugated Polymers of Intrinsic Microporosity C-PIMs) and have SBET values of up to 760 m2 g-1 for homopolymer P77. This value is one of the highest reported values to date for C-PIMs

Luminescent Solar Concentrators Based on Energy Transfer from an Aggregation-Induced Emitter Conjugated Polymer.

Luminescent solar concentrators (LSCs) are solar-harvesting devices fabricated from a transparent waveguide that is doped or coated with lumophores. Despite their potential for architectural integration, the optical efficiency of LSCs is often limited by incomplete harvesting of solar radiation and aggregation-caused quenching (ACQ) of lumophores in the solid state. Here, we demonstrate a multilumophore LSC design that circumvents these challenges through a combination of nonradiative Förster resonance energy transfer (FRET) and aggregation-induced emission (AIE). The LSC incorporates a green-emitting poly(tetraphenylethylene), p-O-TPE, as an energy donor and a red-emitting perylene bisimide molecular dye (PDI-Sil) as the energy acceptor, within an organic-inorganic hybrid diureasil waveguide. Steady-state photoluminescence studies demonstrate the diureasil host induced AIE from the p-O-PTE donor polymer, leading to a high photoluminescence quantum yield (PLQY) of ∼45% and a large Stokes shift of ∼150 nm. Covalent grafting of the PDI-Sil acceptor to the siliceous domains of the diureasil waveguide also inhibits nonradiative losses by preventing molecular aggregation. Due to the excellent spectral overlap, FRET was shown to occur from p-O-TPE to PDI-Sil, which increased with acceptor concentration. As a result, the final LSC (4.5 cm × 4.5 cm × 0.3 cm) with an optimized donor-acceptor ratio (1:1 by wt %) exhibited an internal photon efficiency of 20%, demonstrating a viable design for LSCs utilizing an AIE-based FRET approach to improve the solar-harvesting performance

Understanding the Selection Mechanism of the Polymer Wrapping Technique toward Semiconducting Carbon Nanotubes

Noncovalent functionalization of single-walled carbon nanotubes (SWNTs) using π-conjugated polymers has become one of the most effective techniques to select semiconducting SWNTs (s-SWNTs). Several conjugated polymers are used, but their ability to sort metallic and semiconducting species, as well as the dispersions yields, varies as a function of their chemical structure. Here, three polymers are compared, namely, poly[2,6-(4,4-bis-(2-dodecyl)-4H-cyclopenta[2,1-b;3,4b′]dithiophene)-alt-4,7(2,1,3-ben-zothiadiazole)] (P12CPDTBT), poly(9,9-di-n-dodecylfluorenyl-2,7-diyl) (PF12), and poly(3-dodecylthiophene-2,5-diyl) (P3DDT) in their ability to select two types of carbon nanotubes comprising small (≈1 nm) and large (≈1.5 nm) diameters. P12CPDTBT is a better dispersant than PF12 for small diameter nanotubes, while both polymers are good dispersants of large diameter nanotubes. However, these dispersions contain metallic species. P3DDT, instead presents the best overall performance regarding the selectivity toward semiconducting species, with a dispersion yield for s-SWNTs of 15% for small and 21% for large diameter nanotubes. These results are rationalized in terms of electronic and chemical structure showing that: (i) the binding energy is stronger when more alkyl lateral chains adsorb on the nanotube surface; (ii) the binding energy is stronger when the polymer backbone is more flex-ible; (iii) the purity of the dispersions seems to depend on a strong polymer– nanotube interaction

SmartFilm Tablets for Improved Oral Delivery of Poorly Soluble Drugs

(1) Background: Numerous oral drugs exhibit limited bioavailability due to their poor solubility and poor intestinal permeability. The smartFilm technology is an innovative approach that improves the drug aqueous solubility via incorporating the drug in an amorphous state into a cellulose-based matrix, i.e., paper. smartFilms can be transformed into a free-flowing physical form (i.e., paper granules) that can be compressed into tablets with optimum physico-chemical and pharmaceutical properties. The aim of this study was to investigate if smartFilm tablets are suitable for improved oral delivery of poorly water-soluble drugs. (2) Methods: Curcumin is a poorly soluble drug with low intestinal permeability and was used for the production of curcumin-loaded smartFilms. The curcumin-loaded smartFilms were transferred into smartFilm granules which were then compressed into curcumin-loaded smartFilm tablets. The tablets were characterized regarding their physico-chemical and pharmaceutical properties, and the intestinal permeability of curcumin was determined with the ex vivo porcine intestinal model. The ex vivo intestinal permeability of curcumin from the smartFilm tablets was compared to a physical mixture of curcumin and paper and to a classical and to an innovative commercial product, respectively. (3) Results: The produced curcumin-loaded smartFilm tablets fulfilled the European Pharmacopoeia requirements, incorporated curcumin in amorphous state within the cellulose matrix and exhibited an enhanced dissolution rate. The ex vivo intestinal permeation data were shown to correlate to the in vitro dissolution data. The ex vivo intestinal permeation of curcumin from the smartFilm tablets was about two-fold higher when compared to the physical mixture and the classical commercial product. No differences in the ex vivo bioavailability were found between the smartFilm tablets and the innovative commercial product. (4) Conclusions: smartFilm tablets are a cost-effective and industrially feasible formulation approach for the formulation of poorly water-soluble drugs, i.e., BCS class II and IV drugs

Photothermally Controlled Drug Release of Poly(<span style="font-variant: small-caps">d</span>,<span style="font-variant: small-caps">l</span>-lactide) Nanofibers Loaded with Indocyanine Green and Curcumin for Efficient Antimicrobial Photodynamic Therapy

Chronic wound infections with antibiotic-resistant bacteria have become a significant problem for modern healthcare systems since they are often associated with high costs and require profound topical wound management. Successful wound healing is achieved by reducing the bacterial load of the wound and providing an environment that enhances cell growth. In this context, nanofibers show remarkable success because their structure offers a promising drug delivery platform that can mimic the native extracellular matrix and accelerate cell proliferation. In our study, single-needle electrospinning, a versatile and cost-efficient technique, was used to shape polymers into an applicable and homogeneous fleece capable of a photothermally triggered drug release. It was combined with antimicrobial photodynamic therapy, a promising procedure against resistant bacteria. Therefore, poly(d,l-lactide) nanofibers loaded with curcumin and indocyanine green (ICG) were produced for local antimicrobial treatment. The mesh had a homogeneous structure, and the nanofibers showed a smooth surface. Recordings with a thermal camera showed that near-infrared light irradiation of ICG increased the temperature (>44 °C) in the surrounding medium. Release studies confirmed more than 29% enhanced curcumin release triggered by elevated temperature. The antimicrobial activity was tested against the gram-positive strain Staphylococcus saprophyticus subsp. bovis and the gram-negative strain Escherichia coli DH5 alpha. The nanofibers loaded with both photosensitizers and irradiated with both wavelengths reduced the bacterial viability (~4.4 log10, 99.996%) significantly more than the nanofibers loaded with only one photosensitizer (10, 97.828%) or irradiated with only one wavelength (10, 98.952%). In addition, our formulation efficiently eradicated persistent adhered bacteria by >4.3 log10 (99.995%), which was also confirmed visually. Finally, the produced nanofibers showed good biocompatibility, proven by the cellular viability of mouse fibroblasts (L929). The data demonstrate that we have developed a new economic nanofiber formulation, which offers a triggered drug release, excellent antimicrobial properties, and good biocompatibility