Michal Kawalec

Study of Aliphatic-Aromatic Copolyester Degradation in Sandy Soil and Its Ecotoxicological Impact

Degradation of poly[(1,4-butylene terephthalate)-co-(1,4-butylene adipate)] (Ecoflex, BTA) monofilaments (rods) in standardized sandy soil was investigated. Changes in the microstructure and chemical composition distribution of the degraded BTA samples were evaluated and changes in the pH and salinity of postdegradation soil, as well as the soil phytotoxicity impact of the degradation products, are reported. A macroscopic and microscopic evaluation of the surface of BTA rod samples after specified periods of incubation in standardized soil indicated erosion of the surface of BTA rods starting from the fourth month of their incubation, with almost total disintegration of the incubated BTA material observed after 22 months. However, the weight loss after this period of time was about 50% and only a minor change in the M(w) of the investigated BTA samples was observed, along with a slight increase in the dispersity (from an initial 2.75 up to 4.00 after 22 months of sample incubation). The multidetector SEC and ESI-MS analysis indicated retention of aromatic chain fragments in the low molar mass fraction of the incubated sample. Phytotoxicity studies revealed no visible damage, such as necrosis and chlorosis, or other inhibitory effects, in the following plants: radish, cres, and monocotyledonous oat, indicating that the degradation products of the investigated BTA copolyester are harmless to the tested plants.

Morpholine-functionalized polycarbonate hydrogels for heavy metal ion sequestration

A new six-membered carbonate functionalized with 2-(morpholin-4-yl)ethyl was synthesized and copolymerized with a poly(ethylene oxide)-based cross-linker in a controlled, organocatalyzed ring-opening polymerization process. Well-defined functionalized aliphatic polycarbonate-based hydrogels were obtained with gel fractions reaching 99%. Moreover, the gels that contained 2-(morpholin-4-yl)ethyl groups revealed stimuli-responsive properties towards pH. In the meantime, swelling properties of the hydrogels were found to be reproducible and good stability was observed in the pH range of 4–7.2, while a relatively rapid degradation occurred in more basic solution (pH = 10). ICP MS measurements of aqueous lead(II) nitrate solutions revealed that the functionalized material possessed properties to withdraw and retain lead ions from aqueous solution.

Impact of the Structure of Biocompatible Aliphatic Polycarbonates on siRNA Transfection Ability

RNAi therapeutics are promising therapeutic tools that have sparked the interest of many researchers. In an effort to provide a safe alternative to PEI, we have designed a series of new guanidinium- and morpholino-functionalized biocompatible and biodegradable polycarbonate vectors. The impact of different functions (morpholino-, guanidinium-, hydrophobic groups) of the architecture (linear homopolymer to dumbbell-shape) and of the molecular weight of these copolymers on their capacity to form polyplexes and to decrease the expression of two epigenetic regulators of gene expression, HDAC7 and HDAC5, was evaluated. The use of one of these polymers combining morpholine and guanidine functions at the ratio >1 and hydrophobic trimethylene carbonate groups showed a significant decrease of mRNA and protein level in HeLa cells, similar to PEI. These results highlight the potential of polycarbonate vectors for future in vivo application as an anticancer therapy.

Bioresorbable electrospun nanofibrous scaffolds loaded with bioactive molecules

Abstract Electrospinning technology is used to fabricate sub-micrometric fiber mats made of a random equimolar poly(lactide-co-glycolide) copolymer (PLGA), whose in vitro hydrolytic degradation kinetics is investigated over a period of 49 days in phosphate buffer at 37 °C. The PLGA mats show a decrease of molecular weight (by GPC) from the very beginning of the experiment, whereas a macroscopic weight loss from the samples is appreciated (by gravimetry) only after 20 days of buffer exposure. The molar mass distribution curves remain monomodal during the degradation experiment suggesting that no acid auto-catalyzed hydrolysis, commonly observed in bulk specimens, occurs in sub-micrometric PLGA fibers. PLGA scaffolds containing Endothelial Growth Factor Supplement (ECGS) were also fabricated by electrospinning, from ECGS-containing polymer solutions. Mesenchymal cells derived from human bone marrow mononuclear cells were cultured in the presence of such ECGS-loaded PLGA scaffolds. Flow cytometry and Differential Interference Contrast microscopy were used to characterize the cell cultures over a 7 day period. The results of AnexinV/PI staining and of intranuclear Ki-67 protein expression show, together with concomitant cell morphology modifications, that growth factors released from the scaffolds support the survival, proliferation and growth of the mesenchymal cells. This result demonstrates that ECGS maintains its bioactivity upon release from the electrospun fibers and shows the versatility of the electrospinning technique.