The first successful preparation of chitosan-containing nanofibres was achieved by electrospinning of chitosan/poly(ethylene oxide) (PEO) blend aqueous solutions. The diameters of the nanofibres were in the range 40 -290 nm and decreased with increasing chitosan content and decreasing total concentration. An increase of the applied field strength leads to an increase of the diameter of the nanofibres and to a broadening of the size distribution. The possibility to prepare nanofibres containing a model drug -potassium 5-nitro-8-quinolinolate (K5N8Q), a broad-spectrum antimicrobial and antimycotic agent -was shown. The incorporation of K5N8Q in the nanofibres resulted in a decrease of the nanofibre diameters and the appearance of bead-shaped defects. Non-woven mats from the drugloaded nanofibres with composition chitosan : PEO = 1:1 (w/w) and 1% K5N8Q showed antibacterial and antimycotic activity against E. coli, S. aureus and C. albicans.
Novel well-defined amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly(L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were obtained. The synthesis strategy consisted of a three-step procedure: (i) controlled ring-opening polymerization (ROP) of (D- or L-)lactide initiated by Al(O(i)Pr)(3), followed by (ii) quantitative conversion of the polylactide (PLA) hydroxyl end-groups with bromoisobutyryl bromide and (iii) atom transfer radical polymerization (ATRP) of DMAEMA. The PLA block molecular weight was kept below 5000 g/mol. The macromolecular parameters of the (co)polymers were determined by (1)H NMR spectroscopy and size exclusion chromatography (SEC). The stereocomplexes of PDLA-b-PDMAEMA/PLLA-b-PDMAEMA diblock copolymers were prepared via solvent casting. The stereocomplex formation was evidenced by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The obtained stereocomplexes had melting temperature of about 65 degrees C above that of the individual copolymers and exhibited diffraction patterns assigned to the stereocomplex crystallites. In addition, for the first time it was shown that the replacement of one of the PLA partners with high molecular weight PLLA or PDLA did not hamper the stereocomplex formation. The presence of PDMAEMA blocks proved to impart hydrophilicity of the synthesized copolymers and related stereocomplexes, as determined by static water contact angle measurements.
Novel fibrous materials of stereocomplex between high-molecular-weight poly(d- or l-)lactide (HMPDLA or HMPLLA) and diblock copolymers consisting of poly(l- or d-)lactide and poly(N,N-dimethylamino-2-ethyl methacrylate) blocks, respectively (PLLA-block-PDMAEMA or PDLA-block-PDMAEMA), were prepared by solution electrospinning. Fibers with mean diameters ranging from 1400 to 1700 nm were obtained. The stereocomplex formation was evidenced by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. Annealing at 100 degrees C for 8 h resulted in the appearance of crystalline peaks at 2theta values of 12, 21, and 24 degrees for PLA stereocomplex. X-ray photoelectron spectroscopy (XPS) analyses revealed the gradient composition of the fibers with a surface enriched in tertiary amino groups from PDMAEMA blocks. The availability of tertiary amino groups imparts hemostatic and antibacterial properties to the stereocomplex fibrous materials, as indicated by the performed tests on blood cells and on pathogenic microorganisms.
Poly(L-lactide) (PLLA)/polyethylene glycol (PEG) mixed solutions were successfully electrospun into micro-or nanofibrous polymer mats. The fiber diameter was in the range 100nm-6μm. The effect of the concentration of the spinning solutions and the ratio of PLLA/PEG on the fiber diameter and morphology was investigated. The hydrophilicity was tuned by varying the PLLA/PEG ratio. The tissue compatibility of the electrospun nanofibrous scaffolds was screened using two different cell models of human dermal fibroblasts and the osteoblast-like cell line MG-63. Both types of cells attached uniformly and approximately equally to all PLLA/PEG nanofibers. In long-term cultures osteoblast-like cells tend to spatially organize in tissue-like structure, particularly within the scaffold with the highest PEG content (PLLA/PEG at weight ratio 70/30). These results indicate that PLLA mixed with hydrophilic PEG produces a promising new biocompatible material for engineering scaffolds.
Cover: Non-woven textiles with combined antibacterial and haemostatic activity have been obtained by coating of electrospun poly(L-lactide) mats with chitosan. The mats are promising candidates for wound healing applications enabling rapid cessation of bleeding and regeneration of injured tissue. Further details can be found in the article by M. Spasova, D. Paneva, N. Manolova, P. Radenkov, and I. Rashkov* on page 153.
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