Perfluorophenyl azide functionalization of electrospun poly(para‐dioxanone)

Strategies to surface‐functionalize scaffolds by covalent binding of biologically active compounds are of fundamental interest to control the interactions between scaffolds and biomolecules or cells. Poly(para‐dioxanone) (PPDO) is a clinically established polymer that has shown potential as temporary implant, eg, for the reconstruction of the inferior vena cava, as a nonwoven fiber mesh. However, PPDO lacks suitable chemical groups for covalent functionalization. Furthermore, PPDO is highly sensitive to hydrolysis, reflected by short in vivo half‐life times and degradation during storage. Establishing a method for covalent functionalization without degradation of this hydrolyzable polymer is therefore important to enable the surface tailoring for tissue engineering applications. It was hypothesized that treatment of PPDO with an N‐hydroxysuccinimide ester group bearing perfluorophenyl azide (PFPA) under UV irradiation would allow efficient surface functionalization of the scaffold. X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier‐transformed infrared spectroscopy investigation revealed the successful binding, while a gel permeation chromatography study showed that degradation did not occur under these conditions. Coupling of a rhodamine dye to the N‐hydroxysuccinimide esters on the surface of a PFPA‐functionalized scaffold via its amine linker showed a homogenous staining of the PPDO in laser confocal microscopy. The PFPA method is therefore applicable even to the surface functionalization of hydrolytically labile polymers, and it was demonstrated that PFPA chemistry may serve as a versatile tool for the (bio‐)functionalization of PPDO scaffolds

Functionalizable coaxial PLLA/PDLA nanofibers with stereocomplexes at the internal interface

Multifunctionality of electrospun polylactic acid (PLA) nonwovens was generated by the morphological design of nanofibers. Coaxial fibers with a lower number average molar mass Mn PLLA core and a higher Mn PDLA shell form PDLA–PLLA stereocrystals at the interface, induced by annealing. In tensile tests under physiological conditions, the core–shell fibers with higher crystallinity (22% compared to 11–14%) had lower Young’s moduli E (9 ± 1 MPa) and lower elongation at break εb (26 ± 3%) than PDLA alone (E = 31 ± 9 MPa, εb = 80 ± 5%), which can be attributed to simultaneous crystallization and relaxation effects. Gelatin incorporated in the PDLA phase was presented on the outer surface providing a biointerface putatively favorable for cell adherence. Gelatin incorporation did not influence the crystallization behavior but slightly lowered Tg (60 → 54 °C). Employing exclusively polymers established in the clinic, multifunctionality was generated by design

RGD constructs with physical anchor groups as polymer co-electrospinnable cell adhesives

The tissue integration of synthetic polymers can be promoted by displaying RGD peptides at the biointerface with the objective of enhancing colonization of the material by endogenous cells. A firm but flexible attachment of the peptide to the polymer matrix, still allowing interaction with receptors, is therefore of interest. Here, the covalent coupling of flexible physical anchor groups, allowing for temporary immobilization on polymeric surfaces via hydrophobic or dipole–dipole interactions, to a RGD peptide was investigated. For this purpose, a stearate or an oligo(ethylene glycol) (OEG) was attached to GRGDS in 51–69% yield. The obtained RGD linker constructs were characterized by NMR, IR and MALDI-ToF mass spectrometry, revealing that the commercially available OEG and stearate linkers are in fact mixtures of similar compounds. The RGD linker constructs were co-electrospun with poly(p-dioxanone) (PPDO). After electrospinning, nitrogen could be detected on the surface of the PPDO fibers by X-ray photoelectron spectroscopy. The nitrogen content exceeded the calculated value for the homogeneous material mixture suggesting a pronounced presentation of the peptide on the fiber surface. Increasing amounts of RGD linker constructs in the electrospinning solution did not lead to a detection of an increased amount of peptide on the scaffold surface, suggesting inhomogeneous distribution of the peptide on the PPDO fiber surface. Human adipose-derived stem cells cultured on the patches showed similar viability as when cultured on PPDO containing pristine RGD. The fully characterized RGD linker constructs could serve as valuable tools for the further development of tissue-integrating polymeric scaffolds

Substratum associations of benthic invertebrates in lowland and mountain streams

The preferences of aquatic invertebrate species for specific substrata at the river bottom have been subject of many studies. Several authors classified the substratum preferences of species or higher taxonomic units. Most of these compilations, however, are based on literature analyses and expert knowledge as opposed to the analysis of original data. To enhance our knowledge of invertebrate substratum preferences, we applied a ‘Multi-level pattern’ analysis based on almost 1000 substrate-specific invertebrate samples. The samples were taken in 18 streams in Germany, the Netherlands and Austria, comprising a total of 40 sampling sites and equally covering lowland and mountain streams. The main objectives of our analysis were (I) to derive substratum preferences of taxa in lowland and mountain streams, (II) to compare the preferences with existing data and (III) to compare species substratum associations between lowland and mountain streams. Of the 290 taxa analyzed, 188 were associated significantly to specific substrata. Twenty-five taxa in lowland streams and 51 taxa in mountain streams prefer one or two substratum types (of nine substratum types considered in total). In contrast, 112 species (mountain streams n = 84, lowland streams n = 28) are associated significantly with a broader range of substrata. We compared the classifications derived from our data analysis with those provided in the freshwaterecology.info database (www.freshwaterecology.info). Our results support the existing classifications of substratum preferences in most cases (70%). For 25 species, substratum preferences for both lowland and mountain streams were derived, many of them indicating different substratum associations in the two stream groups. As substratum preferences differed between closely related species, preferences should always be given at the species level as opposed to coarser taxonomic unit